title: Athletic Bilbao signing policy

text: The policy is not written into the Athletic Bilbao rulebook but specific criteria were added to the club's upgraded website in 2008; the approach has become a philosophy of the club in order to promote local players under the (homegrown) system. The policy also extends to Athletic's reserves, their farm team CD Basconia, their youth teams and their women's football department. It does not apply to the coaching staff, with managers from England, Hungary, Germany, France and Argentina among those to have led the team at various times.


title: Athletic Bilbao signing policy

text: They were not the only club to adhere to this approach; Real Sociedad had a similar policy from the late 1960s and won two consecutive league titles in the early 1980s adhering to the self-imposed restriction (as did Athletic), but it was dropped for foreign imports in 1989 when they signed the Republic of Ireland forward John Aldridge, soon followed by their first black player Dalian Atkinson, and they made their first non-Basque Spanish signing in 2002 with the transfer of Boris from Real Oviedo. However, the San Sebastián-based club still places a high importance on producing their own local players, and a high percentage of their squad in the 2010s were home-grown.


title: Athletic Bilbao signing policy

text: The policy has been praised as a symbol of localised football being successful at the highest level, as well as preserving a strong regional identity and being a way for Basque nationalism to be moderately expressed. It has been described as discriminatory for only allowing Basque players to play for Athletic Bilbao, although it has been suggested that the policy is working for them since Athletic are one of only three clubs (along with Real Madrid and Barcelona) never to have been relegated from La Liga.


title: Athletic Bilbao signing policy

text: Due to a relatively low immigrant population in the region, the policy also had the consequence of Athletic Bilbao having been the last club in La Liga to field a black player. That was ended in 2011 when Jonás Ramalho, whose father is Angolan, made his debut. In 2015 Iñaki Williams (born in Bilbao to Ghanaian immigrant parents) became Athletic's first black goalscorer. Prior to Ramalho, in 2000 the first African-born player in the club's youth system was Blanchard Moussayou whose promising career was curtailed by injury; some years later, he stated his belief that it was 'twice as hard' for a black player to make an impact at the club. Gorka Luariz, a forward of mixed ethnicity capped by Equatorial Guinea in 2018, spent time in Athletic's youth system despite being born in Zaragoza as his upbringing was almost entirely in the Basque region. Another international player, Yaser Hamed, born in Biscay to a Palestinian father, spent five years with the club as a child before moving around several local semi-professional teams, playing in the Palestine national football team, and then in Bahraini, Egyptian and Qatari clubs.


title: Athletic Bilbao signing policy

text: Former academy trainee Yuri Berchiche, who rejoined Athletic in the summer of 2018 as one of the club's most expensive signings, has an Algerian father but showed no interest in playing for their national team when the matter was put to him.


title: Athletic Bilbao signing policy

text: As of 2019, Athletic's academy teams included a small number of players of an ethnic minority (mostly Afro-Spaniard) background, including Cameroon-born pair Christophe Atangana (a goalkeeper), and defender Loic Boum who was orphaned as a child and was a ward of the Government of Navarre when he joined the club in 2014 plus forward Nico Williams, the younger brother of Iñaki – he made his first-team debut in 2021. That year, the older youth teams featured a Colombia-born goalkeeper and a handful of locally-born players with African heritage who had mostly been at the club for several years. Malcom Adu Ares, from Bilbao with Bissau-Guinean heritage, made his debut aged 20 in 2022, but he only joined the club a year earlier and had never been part of the setup as a teenager.


title: Athletic Bilbao signing policy

text: The club has also recruited players from the French Northern Basque Country (a region of 300,000 where rugby union is the most popular sport) with Bixente Lizarazu being the first French-Basque to play for the senior team in 1996.


title: Athletic Bilbao signing policy

text: The signing of Aymeric Laporte prompted debate among supporters and columnists regarding the definitions of the policy when he became the first Frenchman to successfully graduate from the club's youth system in 2012, as he had no link to the Basque region through birth or residency, and a blood link only via great-grandparents. He did play for a team in the territory, Aviron Bayonnais, but only by arrangement after the initial approach from Athletic in 2009, as he was too young to move to a club outside France at the time – he arrived formally in 2010.


title: Athletic Bilbao signing policy

text: Yanis Rahmani, a Frenchman of Algerian origin raised in Sestao, progressed as far as Basconia at the same time as Laporte but did not turn professional with the club. Others have progressed no further than youth level.


title: Athletic Bilbao signing policy

text: Antoine Griezmann, the French forward developed by Real Sociedad, was the subject of debate regarding his eligibility for a theoretical move to Athletic as he emerged as an elite player in 2012. Hailing from Burgundy, he arrived at the San Sebastián club aged 14 but only to play football for their academy teams rather than for some other non-sporting reason, and has no connection to the French Basque Country other than attending school there after signing for Real.


title: Athletic Bilbao signing policy

text: The opinions of some (including Athletic's academy director José María Amorrortu) were that his training at a Basque club from a young age adhered to the policy, while others insisted that he had the same (ineligible) status as any adult player transferred in by Real and the other local professional clubs.


title: Athletic Bilbao signing policy

text: In any event, Griezmann showed little interest in joining Athletic, subsequently moved on to Atlético Madrid and was voted the world's third best player in 2016, making any move to Bilbao unlikely in the medium term. In respect of any future players of a similar trajectory, Athletic's position on recruitment remains unconfirmed.


title: Athletic Bilbao signing policy

text: In 1980 the club was believed to have given serious consideration to signing Iker Zubizarreta, a young Venezuelan of Basque heritage (his grandfather Félix played for Athletic in the 1910s) who had impressed at the football tournament at the 1980 Summer Olympics, but decided not to pursue it.


title: Athletic Bilbao signing policy

text: In 2011, media sources claimed that Athletic had shown interest in young Mexican midfielder Jonathan Espericueta but no such move materialised, and the player himself (who did later play in Spain with Villarreal B) stated that his Basque connection was as distant as a great-great-grandfather.


title: Athletic Bilbao signing policy

text: The Uruguayan international Diego Forlán, whose paternal grandmother was from Hondarribia, claimed he had talks over a potential transfer to the club in 2004 but this signing would have been incompatible with the club's stated policy as Forlan was not born in a Basque region, nor did he play football as a youth (or at any point in his career) at a club in the territory. That is also true of Argentinian forward Gonzalo Higuaín and Spaniards Benjamín Zarandona, Kepa Blanco and Jorge López, all players with tenuous Basque links who were also said to have been considered as potential signings by the club's presidential candidates when Athletic were struggling on the field in the mid-2000s under the restrictions of the policy. In 2015 the Australian winger Tommy Oar (with Basque-born grandparents) was the subject of similar speculation, and having been linked to the club at the start of his successful career, Higuain's name was mentioned in the media again 14 years later as he reached veteran status. Multiple UEFA Champions League winner Marco Asensio's Basque father, a former footballer, suggested his son to Athletic as a potential signing early in his career, only to be informed that Mallorca-born Marco did not fit the philosophy. But despite these examples of the rule being applied consistently, Mario Bermejo, a Cantabrian also with a Basque father but trained at Racing Santander, did sign for the club as a promising young player in 1996, which he later stated was smoothed by an Athletic director being an acquaintance of his uncle.


title: Athletic Bilbao signing policy

text: Apart from the occasional anomalies, the typical stance to reject players from the Basque diaspora contrasts with players born in Latin America who were signed by the club such as Marcelino Gálatas, Higinio Ortúzar, Vicente Biurrun, Javier Iturriaga and Fernando Amorebieta who all did have Basque parentage, but as with the small number of players born in other parts of Spain such as Carlos Petreñas, Isaac Oceja, , Armando Merodio, Patxi Ferreira, , , , and Ernesto Valverde, it was primarily their residency in the territory from a young age rather than their ancestry which made them eligible for Athletic. But that was not always the case, as in the 1950s some talented players raised locally but with birthplaces elsewhere (Chus Pereda, Miguel Jones, José Eulogio Gárate and the elder brother of Manuel Sarabia) were not signed as would have been expected in later eras. It has been suggested that the inconsistent rejection of some of these foreign-born players by the club's hierarchy may have been influenced by the ruling regime which emphasised pride in all things Spanish (considering the Basques as part of this single identity), or conversely by some board members' views as Basque nationalists, opposed to Franco in their ultimate aims for their homeland but also involved in judgements on the worthiness of individuals based on their ethnic background.


title: Athletic Bilbao signing policy

text: Conversely, players born in the Basque Country but raised elsewhere are considered eligible. In the years prior to the Spanish Civil War, Athletic undertook a project named 'Operation Return', seeking players born in the Basque region who had emigrated to other countries. One of the few who actually made a competitive appearance for the club was who had begun his career in his adopted homeland of Chile and also played in Mexico before a brief spell in his birthplace. The arrival of Bilbao-born Emilio Aldecoa in 1947 was unusual as he had spent the past decade of his life in England, having been evacuated as a teenage refugee of the Civil War. Another member of that refugee group was the club's star goalkeeper of the era Raimundo Pérez Lezama, although he had returned home much sooner on the outbreak of World War II; a third Basque refugee Sabino Barinaga turned down an offer from Athletic and joined Real Madrid.


title: Athletic Bilbao signing policy

text: Fernando Llorente was born in Pamplona but lived his whole childhood in Rincón de Soto (close to Basque territory but outside it) before he was recruited as an 11-year-old. Two of Athletic's most expensive signings, the Bilbao-born Spain internationals Roberto Ríos and Ander Herrera learned their skills in the cities where their footballing fathers were based professionally (Eusebio at Real Betis of Seville, and Pedro at Real Zaragoza respectively); Gaizka Mendieta (son of Andrés Mendieta of CD Castellón) had similar origins but turned down a move, albeit he remained a proud Basque who played for the unofficial representative team. In 2019, Athletic were reported as enquiring into the availability of young players Gonzalo Desio (the son of former Deportivo Alavés midfielder Hermes Desio, born in Vitoria-Gasteiz but raised in his parents' homeland of Argentina) and Sergio Moreno (born in Pamplona but raised in the Canary Islands and in Madrid, where he made a senior debut with Rayo Vallecano) due to their birthplaces, with no other links tying them to the club's recruitment philosophy.


title: Athletic Bilbao signing policy

text: It was once the case that Athletic would usually recruit from the Biscay province surrounding Bilbao while the other leading clubs Real Sociedad and Osasuna would focus on players from their respective provinces Gipuzkoa and Navarre. In recent decades (with the pool of potential players declining due to a low birth rate in the area), Athletic expanded their recruitment in these other areas in their efforts to accommodate the best players with any Basque links. This saw many talented players from San Sebastián and Pamplona join the club, and also caused Real Sociedad to abandon their own Basque policy in the face of the competition for signings.


title: Athletic Bilbao signing policy

text: Transfers between the clubs increased tensions with Osasuna and with Real; Athletic paid over the odds for players from those rivals on several occasions, including breaking the national record for a native player for Loren in 1989, setting further records for purchasing a teenager with Joseba Etxeberria in 1995 followed by the €6 million outlay on the untested Javi Martínez in 2006, being ordered by courts to pay €5 million for Iban Zubiaurre in 2008 after his signing was found to be a breach of contract, and meeting Iñigo Martínez's €32 million release clause in 2018 (offset by losing Aymeric Laporte the same day in a similar deal worth double that amount).


title: Athletic Bilbao signing policy

text: That change of focus also led to fewer players from the home province being selected; in a 2011 fixture, none of the Athletic starters or used substitutes were from Biscay. However, in subsequent years more local players made the grade, and the situation appears unlikely to occur again in the near future – 12 of the 25 players in the 2016–17 squad were born in Biscay and 14 for the 2019–20 squad, and in November 2017 a study showed that 77% of players in the academy teams hailed from the province.


title: Athletic Bilbao signing policy

text: On the other hand, the definitions of the philosophy are stretched occasionally to accommodate promising youngsters with little Basque connection, which does not always sit well with some of the club's followers.


title: Athletic Bilbao signing policy

text: Enric Saborit, originally from Catalonia, who graduated through the youth and reserve levels to reach the first team, caused questions to be asked when he signed in 2008; he had no connection with the region by birth or blood, but while already 16 years old and playing in RCD Espanyol's "cantera" teams, he moved to Vitoria-Gasteiz where his mother had relocated for work two years earlier. As soon as he became a resident of the territory, Saborit was deemed eligible by Athletic to play for the club. A year earlier, 16-year-old Italian goalkeeper Imanol Schiavella joined the Athletic academy on the strength of his mother being from Andoain, but he departed after two seasons. Three years later Ander Dulce, another youth player with a Basque forename and parent (Jesús Dulce, himself a professional footballer) but born and bred elsewhere – in this case much closer than Schiavella, in Logroño – was also signed, but his promising career was spoiled by serious injury.


title: Athletic Bilbao signing policy

text: In summer 2017, Athletic recruited Youssouf Diarra, an 18-year-old forward born in Mali who was raised in Catalonia and had spent the past two years playing for clubs in Navarre after moving there to continue his education, which the club deemed sufficient under the policy, but apparently decided the circumstances by which Ibrahima Deng, a teenage migrant from Senegal via Tenerife, came to play for Basque club SD Amorebieta did not fit the policy (Deng later joined another local professional club, SD Eibar). The previous year, Athletic had signed 16-year-old Colombia-born defender Deiby Ochoa, who lived in La Rioja and had only ever played for clubs in that region. Like Diarra, he had attended trial matches at the Lezama training centre.


title: Athletic Bilbao signing policy

text: However, despite having invited Ochoa to join, in October 2017 it was announced that the club's youth training camp in Oion (a village in Álava, but just a few miles from Logroño) which was opened in order to create a loophole in their own rule and 'Basque-train' youngsters living close to but not within the region, would no longer accept players who "did not fit the Athletic philosophy", effectively excluding around 150 Riojan youngsters of various ages from the system and leaving only around ten Basques across the squads, indicating a change in approach to youth recruitment among the club hierarchy. Past recruits born in that region, who were considered eligible due to their formative club being Osasuna or Real Sociedad, include José Mari García, Santiago Ezquerro, David López and Borja Viguera; however, the justifications for allowing Luis de la Fuente and later Daniel Aranzubia and Miguel Escalona to join Athletic's youth system directly from Riojan clubs were less clear.


title: Athletic Bilbao signing policy

text: In January 2018, Athletic announced a new signing who was more obviously non-Basque by ethnicity: 25-year-old Cristian Ganea, a Romanian international who was also born in that country and had only played for Romanian clubs for the past five years. But prior to that, he had spent his teenage years living in Basauri just outside Bilbao and had featured for local teams (including Basconia, Athletic's feeder team at semi-professional level who have a separate amateur and juvenile structure), meaning he too was eligible under the 'learned skills at a Basque club' aspect of the policy. A year later, the Bosnian international forward Kenan Kodro joined the club, but his Basque credentials beyond his name (born and raised in San Sebastián and a Real Sociedad youth product) were very robust. Similarly, Ewan Urain was selected by Scotland at under-21 level in 2021 due to his heritage, but was born and raised in Durango, Biscay.


title: Athletic Bilbao signing policy

text: The Athletic Bilbao senior and reserve women's teams were established in 2002. The club won five Spanish championships in its first two decades while adhering to the Basque-only policy, benefitting from the less globalised and commercial nature of the women's game in that period – with less money available for imports, local players predominated across the league's clubs and no Barcelona–Real Madrid duopoly existed, with "Los Blancos" not becoming involved in the sport until 2019. Due to the shorter history of the women's branch there are fewer examples of Athletic players with partial connections to the territory, examples being the internationals Damaris Egurrola (born in Florida, raised in Gernika, later declared for the Netherlands) and Lucía García (born in Barakaldo's specialist maternity hospital as one of a set of quadruplets, raised in Asturias) as well as American goalkeeper Maite Zabala (from the large Basque community in Boise, Idaho) who did not make a competitive appearance. Mention should also be given to Manuela Lareo, of partial Afro-Caribbean (Dominican Republic) descent, who joined the club in 2010 and made her debut later that year, preceding Jonás Ramalho's first appearance for the men's team.


title: Athletic Bilbao signing policy

text: In summer 2019, the club made a signing which many supporters felt was a breach of their code, bringing Germany-born 1.FFC Frankfurt player Bibiane Schulze to Bilbao. As well as marrying into , her mother's family had strong Basque ties, including great-grandfather (Patxo Belaustegigoitia) who played for Athletic a century earlier. Bibiane's personal connections to the region were frequent visits on holiday including informal 'football development' playing on the beach at Lekeitio, and being an Athletic fan as a child. The club president Aitor Elizegi addressed the media to explain the rationale behind the signing, stating she was a player of "clear Basque origin". A year later the club made its first French-Basque women's signing, Sophie Istillart (previously of Bordeaux).


title: Ama Dablam

text: Ama Dablam is a mountain in the eastern Himalayan range of Province No. 1, Nepal. The main peak is , the lower western peak is . Ama Dablam means "Mother's necklace"; the long ridges on each side like the arms of a mother ("ama") protecting her child, and the hanging glacier thought of as the "dablam", the traditional double-pendant containing pictures of the gods, worn by Sherpa women. For several days, Ama Dablam dominates the eastern sky for anyone trekking to Mount Everest Base Camp. For its soaring ridges and steep faces Ama Dablam is sometimes referred as the "Matterhorn of the Himalayas." The mountain is featured in one rupee banknote of Nepal.


title: Ama Dablam

text: Ama Dablam was first climbed on 13 March 1961 by Mike Gill (NZ), Barry Bishop (USA), Mike Ward (UK) and Wally Romanes (NZ) via the "Southwest Ridge". They were well-acclimatised to altitude, having wintered over at 5800 metres near the base of the peak as part of the 1960–61 Silver Hut expedition, led by Sir Edmund Hillary.


title: Ama Dablam

text: Situated at a distance of 162 km north of the provincial capital of Biratnagar and 152 km northeast to Kathmandu, Ama Dablam is the third most popular Himalayan peak for permitted expeditions. The most popular route by far is the "Southwest Ridge" (right skyline in the photo). Prior to a 2006 avalanche, climbers typically set up three camps along the ridge with Camp III just below and to the right of the hanging glacier, the Dablam. Any ice that calves off the glacier typically goes left, away from the camp. However, after the avalanche, climbers now prefer to set just two camps to minimize risk. A climbing permit and a liaison officer are required when attempting Ama Dablam. As with Mount Everest, the best climbing months are April–May (before the monsoon) and September–October.


title: Ama Dablam

text: On the night of 13/14 November 2006, a large serac collapse occurred from the hanging glacier, which swept away several tents at Camp III, killing six climbers (3 European, 3 Sherpa). Eyewitness testimony indicates that Camp III had not been sited in an unusual or abnormally dangerous spot, and that the serac fall was of such magnitude as to render the specific placing of the tents at Camp III irrelevant.


title: Ama Dablam

text: On November 28, 2016, highly acclaimed climbing Sherpa Lakpa Thundu Sherpa of Pangboche was killed when a 5.4 magnitude earthquake struck, triggering an avalanche and the release of a few ice blocks. Thundu was at on the mountain.


title: Ama Dablam

text: On November 11, 2017, Valery Rozov was killed when he jumped from the mountain in a wingsuit and struck a cliff.


title: Ama Dablam

text: A representation of Ama Dablam was originally used by Invesco Perpetual as its branding logo within the UK. It has since been adopted by the INVESCO group of companies as its worldwide signature.


title: Maher-shalal-hash-baz

text: "Maher-shalal-hash-baz" (; , "" – "Hurry to the spoils!" or "He has made haste to the plunder!") was the second prophetic name mentioned in Isaiah chapter 8–9.


title: Maher-shalal-hash-baz

text: The child Maher-shalal-hash-baz is the second prophetic-name child after the birth of Immanuel – traditionally understood as the son of Abi the bride of king Ahaz, "i.e.," the future king Hezekiah, by many Jewish commentators, or of another woman. The phrases "maher-shalal" and "hash-baz" are synonymous, both meaning approximately "quickly to the plunder". The name Maher-shalal-hash-baz is a reference to the impending plunder of Samaria and Damascus by the king of Assyria, Tiglath-Pileser III (734–732 BCE).


title: Maher-shalal-hash-baz

text: This is often counted the longest name (and word) used in the Bible, though a possible longer name-phrase in Isaiah is found in "called Pele-joez-el-gibbor-abi-ad-sar-shalom"


title: Celtis

text: Celtis is a genus of about 60–70 species of deciduous trees, commonly known as hackberries or nettle trees, widespread in warm temperate regions of the Northern Hemisphere. The genus is part of the extended hemp family (Cannabaceae).


title: Celtis

text: "Celtis" species are generally medium-sized trees, reaching tall, rarely up to tall. The leaves are alternate, simple, long, ovate-acuminate, and evenly serrated margins. Diagnostically, "Celtis" can be very similar to trees in the Rosaceae and other rose motif families.


title: Celtis

text: Small flowers of this monoecious plant appear in early spring while the leaves are still developing. Male flowers are longer and fuzzy. Female flowers are greenish and more rounded.


title: Celtis

text: The fruit is a small drupe in diameter, edible in many species, with a dryish but sweet, sugary consistency, reminiscent of a date.


title: Celtis

text: Previously included either in the elm family (Ulmaceae) or a separate family, Celtidaceae, the APG III system places "Celtis" in an expanded hemp family (Cannabaceae).


title: Celtis

text: Members of the genus are present in the fossil record at early as the Miocene of Europe, and Paleocene of North America and eastern Asia.


title: Celtis

text: The generic name originated in Latin and was applied by Pliny the Elder to the unrelated "Ziziphus lotus".


title: Celtis

text: The trees are widespread in warm temperate regions of the Northern Hemisphere, including Southern Europe, South and East Asia, southern and central North America, south and central Africa, and northern and central South America.


title: Celtis

text: Some species, including common hackberry ("C. occidentalis") and "C. brasiliensis", are honey plants and a pollen source for honeybees of lesser importance.


title: Celtis

text: "Celtis" species are used as food plants by the caterpillars of certain Lepidoptera. These include mainly brush-footed butterflies, most importantly the distinct genus "Libythea" (beak butterflies) and some Apaturinae (emperor butterflies):


title: Celtis

text: The plant pathogenic basidiomycete fungus "Perenniporia celtis" was first described from a "Celtis" host plant. Some species of "Celtis" are threatened by habitat destruction.


title: Celtis

text: Several species are grown as ornamental trees, valued for their drought tolerance. They are a regular feature of arboreta and botanical gardens, particularly in North America. Chinese hackberry ("C. sinensis") is suited for bonsai culture; a magnificent specimen in Daegu-myeon is one of the natural monuments of South Korea. The berries are generally edible when they ripen and fall. "C. occidentalis" fruit was used by the Omaha, eaten casually, as well as the Dakota people, who pounded them fine, seeds and all. The Pawnee used the pounded fruits in combination with fat and parched corn.


title: Celtis

text: Hackberry wood is sometimes used in cabinetry and woodworking. The berries of some, such as "C. douglasii", are edible, and were consumed by the Mescalero Apaches.


title: 2008 in video games

text: 2008 has seen many sequels and prequels in video games. New intellectual properties (IPs) include "Army of Two", "Dead Space", "iRacing", "Left 4 Dead", "LittleBigPlanet", "Mirror's Edge", "", and "Spore".


title: 2008 in video games

text: The following are the best-selling games of 2008 in terms of worldwide retail sales. These games sold at least units worldwide in 2008.


title: 2008 in video games

text: Best-selling video games in Japan, United Kingdom, and the United States combined (January–July 2008)


title: Bess Myerson

text: Bess Myerson (July 16, 1924 – December 14, 2014) was an American politician, model and television actress who in 1945 became the first Miss America who was also Jewish.


title: Bess Myerson

text: Her achievement, in the aftermath of the Holocaust, was seen as an affirmation of the Jewish place in American life. She was a heroine to parts of the Jewish community, where "she was the most famous pretty girl since Queen Esther."


title: Bess Myerson

text: Myerson made frequent television appearances during the 1950s and 1960s. She was a commissioner in the New York City government, served on presidential commissions from the 1960s through the 1980s, and ran unsuccessfully for the U.S. Senate. Her career in public service ended in the late 1980s when she was indicted on bribery and conspiracy charges. She was acquitted after a highly publicized trial.


title: Bess Myerson

text: Myerson was born in The Bronx, New York to Louis Myerson and Bella (née Podell), who were Jewish immigrants from Russia. Myerson's father worked as a housepainter, handyman, and carpenter. After Myerson's birth, the family moved from the South Bronx to Shalom Aleichem Houses, a cooperative apartment complex in the northern Bronx. She had three siblings: a younger sister, Helen; an elder sister, Sylvia; and a brother, Joseph, who died at the age of three before Myerson was born.


title: Bess Myerson

text: Her upbringing emphasized the importance of scholarship, not physical beauty. In addition to tradesmen, her neighbors included poets, writers, and artists. Myerson reached her adult height when she was 12 and towered over other children, something she said made her feel "awkward and gawky" during her preadolescence. Myerson recalled one of her worst childhood memories was playing the Popeye character Olive Oyl in an elementary school play.


title: Bess Myerson

text: Myerson began studying piano when she was nine years old and was in the second class of New York's High School of Music and Art in 1937, graduating in 1941. She went on to Hunter College, graduating with honors in 1945 with a Bachelor of Arts degree in music. To support herself and her family while in college she gave piano lessons for fifty cents an hour, and worked as a music counselor at a girl's summer camp in Vermont.


title: Bess Myerson

text: By the time she was 21, Myerson was tall with "luxuriant brown hair". Myerson was entered into the Miss New York City competition, without her knowledge, by John C. Pape, a retired steel magnate and amateur photographer who had employed her as a model while she was in college. When Myerson was told about the pageant by her sister, Sylvia, who was acquainted with Pape, Myerson was angry as she felt that the beauty business was "embarrassing." However, she was persuaded to compete by Sylvia, and she competed in the swimsuit competition using a borrowed bathing suit.


title: Bess Myerson

text: Myerson went on to enjoy competing in the pageant, in which she stood out from the other contestants because of her height. On August 15, 1945, the day of Japan's surrender (VJ Day), she won the competition for the pageant, and moved on to the Miss America competition, partly motivated by the $5,000 scholarship awarded to the winner. She later told interviewers she wanted to buy a black Steinway grand piano with the scholarship money.


title: Bess Myerson

text: Myerson was the Miss New York entry in the 1945 Miss America pageant, and she competed in the talent portion of the contest by performing the music of Edvard Grieg and George Gershwin. Prior to the competition, she was pressured to use a pseudonym that "sounded less Jewish." Despite revelations of the Holocaust in the previous months, America was still widely perceived as a Anglo-Saxon Protestant society which manifested hostility towards people of Jewish ancestry. Myerson refused, and was subjected to substantial antisemitism. After she won the title on September 8, 1945, three of the pageant's five sponsors withdrew from having her represent their companies as Miss America.


title: Bess Myerson

text: She paid for graduate studies at Juilliard and Columbia University with the pageant scholarship money. An aspiring pianist, she briefly gave recitals on the vaudeville circuit before realizing audiences were more interested in seeing her in a bathing suit. She also played with the New York Philharmonic and appeared at Carnegie Hall.


title: Bess Myerson

text: While Myerson was on her year-long tour as Miss America, she encountered "No Jews" signs posted in places such as hotels and country clubs. Such experiences led her to conduct lectures on behalf of the Anti-Defamation League titled "You Can't Be Beautiful and Hate". Myerson became a vocal opponent of antisemitism and racism, and her speaking tour became the highlight of her Miss America reign.


title: Bess Myerson

text: Religion News Service observed that at the time that she won the pageant, emaciated concentration camp survivors had only just shed their prison clothes. "Bess Myerson represented the resurrection of the Jewish body—the journey from degradation to beauty."


title: Bess Myerson

text: A few years after hearing her speak at an ADL function, television producer Walt Framer hired Myerson for the 1950s game show "The Big Payoff". She was the "Lady in Mink" modeling the grand prize mink coat, and introducing guests and prizes, throughout the 1951 to 1959 network run of the program. Recognized for her wit and hard work, in 1954 Myerson was a panelist on the game show "The Name's the Same" and from 1958 through 1967 a panelist on "I've Got a Secret". She regularly substituted for Dave Garroway on the "Today Show". She was also a host of the television broadcast of the Miss America pageant from 1954 to 1968.


title: Bess Myerson

text: Myerson stepped down from her other commitments in 1969 when appointed by Mayor John V. Lindsay to become the first Commissioner of the New York City Department of Consumer Affairs. Her career as a commercial pitchwoman for a number of products throughout the 1950s and 1960s had led to her becoming a consultant to several consumer products companies. In her consumer affairs position, which she held until 1973, she became a pioneer in consumer protection law.


title: Bess Myerson

text: She also served on several presidential commissions on violence, mental health, workplace issues, and hunger in the 1960s and 1970s. Myerson was a frequent public companion of then-Congressman Ed Koch throughout the late 1970s and the beginning of his mayoral ambitions, and later chaired his successful 1977 campaign for New York City mayor.


title: Bess Myerson

text: In the 1980 United States Senate election, Myerson vied for the Democratic nomination in New York against Congresswoman Elizabeth Holtzman, Queens District Attorney John J. Santucci, and Lindsay. Myerson lost to Holtzman by a wide margin. Holtzman was subsequently defeated by Al D'Amato.


title: Bess Myerson

text: In 2002, Myerson appeared in the documentary film "Miss America" as a former Miss America interviewee.


title: Bess Myerson

text: After serving in the Koch administration in 1983 as Commissioner of the Department of Cultural Affairs, Myerson's career became overshadowed by controversy. She became romantically involved with a married sewer contractor, Carl Andrew Capasso. It soon emerged that Hortense Gabel—the judge involved in Capasso's divorce case—had started socializing with Myerson. Judge Gabel's daughter (Sukhreet) was also hired by Myerson. After Gabel cut Capasso's child support payments, investigations began as to whether or not Gabel had been bribed. In April 1987, after Myerson invoked the Fifth Amendment, she was forced to resign her position with the Koch administration. The scandal became known as the "Bess Mess."


title: Bess Myerson

text: Myerson, Capasso, and Gabel were indicted a year later and tried on federal charges of conspiracy, mail fraud, obstruction of justice, and using interstate facilities to violate state bribery laws, accused of conspiring to reduce Capasso's child support payments. With Sukhreet as the prosecution's chief witness, the main issue at the U.S. District Court trial was whether Myerson's decision to hire Sukhreet constituted bribery. After four months of trial proceedings, all three defendants were acquitted. Capasso remained in prison, having previously been convicted of unrelated tax charges.


title: Bess Myerson

text: In October 1946, Myerson married Allan Wayne, a recently discharged U.S. Navy captain. They had one daughter, Barbara, born in 1948. The marriage was marred by domestic violence, and the couple divorced after eleven years. Myerson's second marriage was to attorney Arnold Grant, and he legally adopted her daughter in 1962. The couple divorced in the early 1970s. Daughter Barbara later became an actress, director, and screenwriter who is now known as Barra Grant.


title: Bess Myerson

text: Before her federal trial began, Myerson was arrested in May 1988 for shoplifting at a department store in South Williamsport, Pennsylvania. She pleaded guilty to retail theft and was ordered to pay a fine.


title: Bess Myerson

text: Myerson was very connected with her Jewish roots and was filmed in conversation with the Lubavitcher Rebbe. She donated funds to help build "Bessie's Bistro" at the Jewish Museum of Florida-FIU in memory of her parents Bella and Louis Myerson who lived in the neighborhood near the Museum.


title: Bess Myerson

text: Myerson survived ovarian cancer in the 1970s and experienced a mild stroke in 1981, from which she made a full recovery. She moved to Florida in 2002, and later moved to California, where she remained until her death. In 2013, she was reported to be suffering from dementia.


title: Bess Myerson

text: Myerson died on December 14, 2014, in Santa Monica, California, at age 90. Her death was not immediately announced publicly, but it was confirmed by the Los Angeles County Coroner's Office three weeks after she died. She was interred at Woodlawn Cemetery in Santa Monica.


title: Romana (Doctor Who)

text: Romana, short for Romanadvoratrelundar (), is a fictional character in the long-running British science fiction television series "Doctor Who". A Time Lord from the planet Gallifrey, she is a companion to the Fourth Doctor.


title: Romana (Doctor Who)

text: As a Time Lord, Romana is able to regenerate, having had two on-screen incarnations with somewhat different personalities (dubbed Romana I and Romana II by fans). Romana I was played by Mary Tamm from 1978 to 1979. When Tamm chose not to sign on for a second season, the part was recast. Romana II was played by Lalla Ward from 1979 to 1981. A third incarnation of Romana has been depicted in some of the spin-off novels, and a fourth (performed by Juliet Landau) has been featured in several audio dramas released by Big Finish Productions in 2013 and 2014, and appeared again in early 2015.


title: Romana (Doctor Who)

text: Romana is one of only two members of the Doctor's own race to travel with him in the original television series, the first being his granddaughter Susan Foreman (though the term "Time Lord" was only introduced after Susan's departure).


title: Romana (Doctor Who)

text: The White Guardian originally assigns Romana to assist the Doctor during the quest for the Key to Time, a series of linked serials which constitute the whole of Season 16 (1978–79). Romana first appears in "The Ribos Operation", and was intended as a contrast to her predecessor, the savage Leela. Romana is initially haughty and somewhat arrogant, looking down on the Doctor (whom she considers to be her academic inferior) and responding to his initial resentment at her presence with icy put-downs. However, she soon gains an appreciation for the Doctor's experience and sense of adventure, and begins to respect him as a teacher.


title: Romana (Doctor Who)

text: Over the course of Season 16, Romana begins to take on some of the characteristics of the screaming "damsel in distress", which reinforced Tamm's decision not to remain in the role as she felt the character had been taken as far as she could go. As a result, Romana regenerates at the start of Season 17, emerging with a different physical appearance and a lighter personality.


title: Romana (Doctor Who)

text: Although Tamm had left the show on relatively good terms and was willing to film a regeneration sequence for the start of Season 17, she was not invited to do so. There was a rumour, purportedly started by former producer John Nathan-Turner, that the real reason Tamm left was that she was pregnant. Tamm has denied this repeatedly over the years.


title: Romana (Doctor Who)

text: The introduction of Romana's second incarnation at the start of "Destiny of the Daleks" — a script credited to Terry Nation, but with several additions and alterations by script editor Douglas Adams — treats the concept of regeneration humorously; Romana changes bodily forms several times, rather like someone casually trying on different outfits, before deciding to take the form of Princess Astra, who had been played by Lalla Ward in the final serial of Season 16, "The Armageddon Factor". This regeneration scene is controversial with some fans, as it does not conform to the seriousness with which regeneration is presented in most other cases. It is generally presented as traumatic, even emotionally or physically agonizing. Attempts at rationalising Romana's regeneration have been made in licensed spin-off media, including the "Short Trips" short story "The Lying Old Witch in the Wardrobe" which speculates that the TARDIS was responsible for her regeneration. It has also been theorised that Romana may have needed to regenerate after being tortured by the Shadow in the previous serial, and that the different bodies she tries were merely projections.


title: Romana (Doctor Who)

text: The second Romana enjoys a more intimate relationship with the Doctor than her previous incarnation, to the point that some fans have assumed a romantic relationship with the Doctor. Although a relationship was never explicitly shown or intended by the writers, many fans have found the signs of a romantic relationship particularly evident in the story "City of Death", perhaps reflecting the real-life romance between Tom Baker and Lalla Ward which blossomed during the production of that story, leading to their brief marriage in 1980. In many ways, she might be claimed to be the companion most like her Doctor (if Romana I were not more like the Doctor than her) – besides being of the same race and comparable intelligence, she occasionally mimics his sense of style, wields her own sonic screwdriver and can occasionally get the better of him in moments of banter and more practical situations. As her practical experience develops, she also becomes more assured and capable in the situations she encounters.


title: Romana (Doctor Who)

text: At the end of the serial "Meglos", Romana receives word from the Time Lords recalling her to Gallifrey. The opening of the next serial "Full Circle" makes it clear that, having travelled with the Doctor, she no longer desires to return home. Before the issue can be resolved, the TARDIS falls through a "charged vacuum emboitment" and disappears into another universe known as E-Space. Her final television appearance was in the 1981 story "Warriors' Gate" where, along with the robot dog K9, she leaves to forge her own path in E-space when faced with a choice of remaining there or returning to Gallifrey. She also appears briefly in the 20th Anniversary special "The Five Doctors" through the reuse of footage from the uncompleted story "Shada", as Tom Baker declined to film any new scenes for the special.


title: Romana (Doctor Who)

text: After the departure of both Romana I and II, both versions of the character also appeared very briefly in flashback sequences during the Fourth Doctor's regeneration in "Logopolis" as well as the Fifth Doctor's mind-copy in "Resurrection of the Daleks". Romana would also be mentioned in "Castrovalva" during the Fifth Doctor's post-regenerative confusion, as well as in "Arc of Infinity", in which the Fifth Doctor, in response to a reprimand from the High Council of Time Lords for "leaving [her] behind", retorts that she "chose to remain in E-Space". Ward subsequently returned for a brief cameo as Romana in the 1993 charity special "Dimensions in Time".


title: Romana (Doctor Who)

text: Outside of the television programme, the Fourth Doctor and Romana II also appear in Australian-filmed television advertisements for PR1ME Computer, Inc. in 1980, which played in a tongue-in-cheek way with the idea that the two characters shared a romantic relationship, climaxing with the Doctor proposing marriage (which occurred in real life between Tom Baker and Lalla Ward after her departure from the series that same year).


title: Romana (Doctor Who)

text: An article by Russell T Davies in the "Doctor Who Annual 2006" states that Romana was President of the Time Lords during the Last Great Time War against the Daleks (see below), which ended with Gallifrey being destroyed. As with all spin-off media, its canonicity in relation to the television series is debatable.


title: Romana (Doctor Who)

text: In the licensed Virgin New Adventures novel "Blood Harvest" by Terrance Dicks, Romana II leaves E-Space and returns to Gallifrey with the help of the Seventh Doctor. In "Goth Opera" by Paul Cornell, from the complementary Missing Adventures series, she is given a seat on the High Council of Time Lords. In New Adventures' "Happy Endings", also by Cornell, it is revealed that Romana has become Lady President of Gallifrey. Romana's presidency is reflected in the later novels and in her appearances (voiced by Ward) in audio dramas from Big Finish Productions. She also makes a cameo appearance in "Human Nature" in a vision. Romana appears in the unlicensed fan fiction novel "Time's Champion", in the role of President of the Time Lords.


title: Romana (Doctor Who)

text: Romana's appearance in the 1997 novel "The Eight Doctors"- where she helps the newly regenerated Eighth Doctor rescue his fourth incarnation from a group of vampires in the aftermath of "State of Decay"- was highlighted in a trailer for the re-launched "Doctor Who" range which was included on a number of BBC videos in 1997-8. The trailer used a clip from "Destiny of the Daleks" to illustrate Romana.


title: Romana (Doctor Who)

text: Romana's time with the Doctor is also explored in several novels, which include additional adventures for her first incarnation when outside forces divert their efforts to find the Key to Time and general adventures for her second incarnation prior to departing in E-space.


title: Romana (Doctor Who)

text: In the BBC Books Eighth Doctor Adventures novels, Romana undergoes a second regeneration, and her new incarnation (Romana III, whose appearance was modelled on silent movie actress Louise Brooks) is far less sympathetic and far more ruthless than the other two. This third incarnation pursues the Eighth Doctor in a story arc relating to the Future War, a War between the Time Lords and an as-yet-unidentified enemy, seeking to use his new companion Compassion – who has been unintentionally mutated into a Type 102 TARDIS in the aftermath of the destruction of the Doctor's own ship – as breeding stock for the new sentient TARDISes in the Future War. With the Doctor refusing to allow the Time Lords to make Compassion a slave, he, Compassion and fellow companion Fitz Kreiner go on the run between "The Shadows of Avalon" and "The Ancestor Cell", the final confrontation on board the Doctor's believed-destroyed original TARDIS resulting in the obliteration of Gallifrey and the apparent retroactive wiping out of the Time Lords from history. A flashback in the final Eighth Doctor Adventures novel "The Gallifrey Chronicles" suggests that Romana is killed by Faction Paradox skulltroopers just before Gallifrey's destruction. However, it is hinted in "Tomb of Valdemar" by Simon Messingham that Romana may be one of a few Time Lords who survived this cataclysm, possibly in a fourth incarnation and "The Gallifrey Chronicles" itself suggests that the Doctor will eventually restore Gallifrey and all the dead Time Lords whose minds are stored in the Matrix, in time for its destruction again in the Time War.


title: Romana (Doctor Who)

text: Romana II appeared pseudonymously in a series of audio plays produced in the early 2000s by BBV. In this series, Lalla Ward played a character who appeared with K9 in an unnamed parallel universe. This character is called the Mistress (which was what K9 called Romana in the television series). Because of an unusual copyright situation in which BBV was able to license K9 but not Romana or other "Doctor Who" elements, the Mistress is not explicitly called Romana. For similar reasons, the parallel universe (obviously intended to reflect Romana's exile in E-Space) is called a "pocket universe" in the series' packaging.


title: Romana (Doctor Who)

text: In Big Finish's regular line of "Doctor Who" audio stories, Ward joined Colin Baker's Sixth Doctor in "The Apocalypse Element", in which Romana is Lady President of Gallifrey. In the story, it is revealed that Romana II was abducted by the Daleks soon after assuming the presidential office, and remained in captivity for twenty years before making her escape, briefly reuniting with the Doctor before reassuming her post. Romana II also appears with Paul McGann's Eighth Doctor in the 2003 remake of "Shada", an audio play produced by Big Finish for the BBC's "Doctor Who" website and accompanied by Macromedia Flash animations, and also in "Neverland" and "Zagreus". More recently, she has appeared with the Fifth Doctor in "The Chaos Pool", the final part of the "Key 2 Time" trilogy, where it is revealed that Romana's regeneration was at least partly caused by her transformation into the new sixth segment of the Key to Time, the audio concluding with the segment's essence being transferred back to Astra to save Romana's life before the Doctor destroys the Key for good.


title: Romana (Doctor Who)

text: In "Neverland" Romana encounters the Eighth Doctor as Anti-Time infects the Universe. With other Time Lords she travels to the Anti-Verse in the hope of finding a way to stop the flow of Anti-Time. But there she is left by Co-ordinator Vansell to the Neverpeople, those the Time Lords have erased from existence, who are planning to send Anti-Time to Gallifrey. However she helps the Doctor activate the TARDIS and stop the Anti-Time. In the sequel to this "Zagreus", Romana II is forced to banish the Eighth Doctor from the universe as he has become a danger to it following his infection by the forces of "anti-time". Following on from this, she is featured in a number of audio plays with former Doctor companion Leela (played by Louise Jameson) under the umbrella title of "Gallifrey".


title: Romana (Doctor Who)

text: In the audio series, Romana has to contend with the emergence of a terrorist group known as Free Time, which wants to break the technological monopoly on time travel and threatens not just Gallifrey, but its time travel-capable allies. Romana's progressive policies, including opening the Academy to non-Gallifreyans, also face opposition from more conservative elements. Complicating this is the escape of an ancient evil called Pandora from the Matrix in the paradoxical form of Romana's first incarnation (played once again by Mary Tamm). Both Romana and the Pandora entity proclaim themselves Imperiatrix of Gallifrey, provoking a civil war. At the war's end, Romana destroys Pandora by trapping her in the Matrix and destroying it. She is also removed from the Presidency. With Gallifrey on the brink of economic and social collapse, as well as in danger of being overrun by a Free Time virus, Romana and her friends flee through several alternate universes. Romana encounters many versions of Gallifrey worse than her own, before finally becoming trapped in one. This Gallifrey is similar, but without the ability to time travel. After their President Romana is assassinated, she assumes her identity, regaining her office, albeit in a different universe. She is eventually able to return to her universe with a cure for the Free Time virus, although the audios then lead into early strikes by the Daleks that are apparently intended to foreshadow the Time War.


title: Romana (Doctor Who)

text: Big Finish's spin-off line "The Companion Chronicles" has featured new performances by both Ward and Tamm in a number of stories set within their respective continuities.


title: Romana (Doctor Who)

text: Tamm reprised the role of Romana for the final time alongside Tom Baker for a second series of original audio dramas (the first series having featured Leela) set after the Key to Time era. Recorded several months before Tamm's death in 2012, the first of these, "The Auntie Matter", was released in January 2013, with a total of seven plays being released up until July 2013.


title: Romana (Doctor Who)

text: In July 2013 it was announced that Juliet Landau would play a future incarnation of Romana for Big Finish. This version of Romana was introduced in "Renaissance", the third chapter of "Gallifrey VI", released in October 2013, and was said to come from thousands of years in the future. This version of Romana was later reprised by Landau in the January 2014 audio drama "Luna Romana", part of Big Finish's "Companion Chronicles" line; Landau also performs the role of Romana I in lieu of the now-deceased Mary Tamm in this story, the narrative intending to present Landau's Romana as looking back on the events of her first incarnation's travels with the Doctor. To avoid confusion with her earlier self, this future Romana volunteers to use the name Lady Trey (taken from one of the middle syllables of her full name). Landau returned to the role once again in "Gallifrey: Intervention Earth", a continuation of the "Gallifrey" series released in January 2015. This story is revealed in the follow-up "Enemy Lines" to depict what happens shortly after Ward’s incarnation is forced to regenerate and sees Gallifrey on the brink of another war. However Irving Braxiatel prevents the regeneration so that these events, including the very existence of the Landau incarnation, are undone.


title: Romana (Doctor Who)

text: In November 2013 it was revealed that Lalla Ward would reprise her role of Romana II alongside former Fourth Doctor Tom Baker and John Leeson as K9 in a pair of audio adaptations of Gareth Roberts Missing Adventure novels "The Romance of Crime" and "The English Way of Death" in January 2015, to be followed by at a series of new adventures in 2016 and another in 2017. There is no word yet if this will be followed by a third in 2018. Lalla Ward also returned as Romana II in "Gallifrey: Enemy Lines" in 2016, "Gallifrey: Time War I" in 2018, "Gallifrey: Time War II" in 2019, "Gallifrey: Time War III" in 2020 and "Gallifrey: Time War IV" in 2021.


title: Romana (Doctor Who)

text: During the opening of Destiny of the Daleks three rejected incarnations of Romana were played by uncredited actresses Maggie Armitage, Yvonne Gallagher and Lee Richards


title: Allegations of United States support for the Khmer Rouge

text: The United States (U.S.) voted for the Khmer Rouge and the Khmer Rouge-dominated Coalition Government of Democratic Kampuchea (CGDK) to retain Cambodia's United Nations (UN) seat until as late as 1993, long after the Khmer Rouge had been mostly deposed by Vietnam during the 1979 Vietnamese invasion of Cambodia and ruled just a small part of the country. It has also been reported that the U.S. encouraged the government of China to provide military support for the Khmer Rouge. There have also been related allegations by several sources, notably Michael Haas, which claim that the U.S. directly armed the Khmer Rouge in order to weaken the influence of Vietnam and the Soviet Union in Southeast Asia. These allegations have been disputed by the U.S. government and by journalist Nate Thayer, who argued that little, if any, American aid actually reached the Khmer Rouge.


text: The Khmer Rouge, the communist party led by Pol Pot, came to power in 1975 during the Cambodian Civil War, which was linked to the Vietnam War. They defeated the Khmer Republic, who were heavily supported by the U.S., including a massive bombing campaign against the Khmer Rouge until 1973. North Vietnam, who had many soldiers in Cambodia, and China were the primary backers of the Khmer Rouge during the civil war. Between 1975 and 1979, the Khmer Rouge perpetrated the Cambodian genocide, which killed between 1.5 and 2 million people, nearly 25% of Cambodia's population. During the genocide, China was the main international patron of the Khmer Rouge, supplying "more than 15,000 military advisers" and most of its external aid.


text: Vietnam invaded Cambodia in late 1978 and established the People's Republic of Kampuchea (PRK) led by Khmer Rouge defectors. Vietnam's invasion was motivated by repeated cross-border attacks by the Khmer Rouge that targeted Vietnamese civilians, including the Ba Chúc massacre—in which the Khmer Rouge systematically killed the entire population of a Vietnamese village of over 3,000 people, with the exception of one woman who survived being shot in the neck and clubbed, causing her to suffer painful headaches for the rest of her life; before being killed, many of the victims were "barbarously tortured." These attacks killed over 30,000 Vietnamese in total.


text: Vietnam ousted the Khmer Rouge and ended the genocide in a mere 17 days, and Vietnamese troops occupied Cambodia for the next eleven years. Following the invasion, Vietnam attempted to publicize the crimes of the Khmer Rouge, establishing an ossuary for the victims at Ba Chúc and convincing the PRK to do the same for the Khmer Rouge's Cambodian victims; the Khmer Rouge's most notorious prison, S-21—which held 20,000 prisoners, "all but seven" of whom were killed—was revealed in May 1979 and eventually turned into the Tuol Sleng Genocide Museum, although there were well over 150 Khmer Rouge death camps "on the same model, at least one per district."


text: To punish Vietnam for overthrowing the Khmer Rouge, China invaded Vietnam in February 1979, while the United States (U.S.) "merely slapped more sanctions on Vietnam" and "blocked loans from the International Monetary Fund [(IMF)] to Vietnam."


text: China trained Khmer Rouge soldiers on its soil during 1979—1986 (if not later), "stationed military advisers with Khmer Rouge troops as late as 1990," and "supplied at least $1 billion in military aid" during the 1980s. After the 1991 Paris Peace Accords, Thailand continued to allow the Khmer Rouge "to trade and move across the Thai border to sustain their activities ... although international criticism, particularly from the U.S. and Australia ... caused it to disavow passing any direct military support."


text: As a result of Chinese and Western opposition to the Vietnamese invasion and occupation of Cambodia, the Khmer Rouge, rather than the PRK, was allowed to hold Cambodia's United Nations (UN) seat until 1982. After 1982, the UN seat was filled by a Khmer Rouge-dominated coalition—the Coalition Government of Democratic Kampuchea (CGDK). Owing to Chinese, U.S., and Western support, the Khmer Rouge-dominated CGDK held Cambodia's UN seat until 1993, long after the Cold War had ended.


text: In 1998 former U.S. National Security Advisor (NSA) Zbigniew Brzezinski acknowledged that "I encourage[d] the Chinese to support Pol Pot ... we could never support him, but China could." However, Brzezinski subsequently stated: "The Chinese were aiding Pol Pot, but without any help or arrangement from the United States. Moreover, we told the Chinese explicitly that in our view Pol Pot was an abomination and that the United States would have nothing to do with him—directly or indirectly."


text: In late 1975, U.S. NSA and Secretary of State Henry Kissinger told the Thai foreign minister: "You should tell the Cambodians that we will be friends with them. They are murderous thugs but we won't let that stand in our way." In 1998 Kissinger elaborated: "The Thais and the Chinese did not want a Vietnamese-dominated Indochina. "We" didn't want the Vietnamese to dominate. I don't believe we did anything for Pol Pot. But I suspect we closed our eyes when some others did something for Pol Pot."


text: Cambodian leader Norodom Sihanouk, when asked about charges of opportunism in May 1987 (""your critics would say ... that you would sleep with the Devil to achieve your end""), replied: "As far as devils are concerned, the U.S.A. also supports the Khmer Rouge. Even before the forming of the Coalition Government in 1982, the U.S. each year voted in favor of the Khmer Rouge regime. ... The U.S.A. says that it is against the Khmer Rouge, that it is pro-Sihanouk, pro-Son Sann. But the devils, they are there ["laughs"] with Sihanouk and Son Sann."


text: According to Tom Fawthrop, U.S. support for the Khmer Rouge guerrillas in the 1980s was "pivotal" to keeping the organization alive, and was in part motivated by revenge over the U.S. defeat during the Vietnam War. A WikiLeaks dump of 500,000 U.S. diplomatic cables from 1978 shows that the administration of President Jimmy Carter was torn between revulsion at the atrocities of the Khmer Rouge and concern with the possibility of growing Vietnamese influence should the Khmer Rouge collapse.


text: According to Michael Haas, despite publicly condemning the Khmer Rouge, the U.S. offered military support to the organization and was instrumental in preventing UN recognition of the Vietnam-aligned government. Haas argued that the U.S. and China responded to efforts from the Association of South East Asian Nations (ASEAN) for disarming the Khmer Rouge by ensuring the Khmer Rouge stayed armed, and that U.S. efforts for merging the Khmer Rouge with allied factions resulted in the formation of the CGDK. After 1982, the U.S. increased its annual covert aid to the Cambodian resistance from $4 million to $10 million. Haas's account is corroborated by Singaporean diplomat Bilahari Kausikan, who recalled: "ASEAN wanted elections but the U.S. supported the return of a genocidal regime. Did any of you imagine that the U.S. once had in effect supported genocide?" Kausikan described the disagreement between the U.S. and ASEAN over the Khmer Rouge as reaching the threshold that the U.S. threatened Singapore with "blood on the floor".


text: By contrast, Nate Thayer recounted that "The United States has scrupulously avoided any direct involvement in aiding the Khmer Rouge", instead providing non-lethal aid to non-communist Khmer People's National Liberation Front (KPNLF) and Armee Nationale Sihanouk (ANS) insurgents, which rarely cooperated with the Khmer Rouge on the battlefield, despite being coalition partners, and which fought with the Khmer Rouge dozens of times prior to 1987. According to Thayer, "In months spent in areas controlled by the three resistance groups and during scores of encounters with the Khmer Rouge ... I never once encountered aid given to the [non-communist resistance] in use by or in possession of the Khmer Rouge."


text: Although U.S. policy was to provide support to "15,000 ineffective 'noncommunist' rebel fighters", Joel Brinkley stated that "charges made the rounds that some of the American aid, $215 million so far, was finding its way to the Khmer Rouge." A subsequent investigation led by Thomas Fingar of the State Department's Bureau of Intelligence and Research (INR) "found some leakage—including sharing of ammunition, joint defense of a bridge, and using one truck to transport both 'noncommunist' and Khmer Rouge fighters to a fight." Fingar was dismissive of his own investigators's report, which he characterized as an "epiphenomenon in a flea circus": "Isn't the larger objective here defeating the Vietnamese puppets in Phnom Penh?"


title: Ohio's congressional districts

text: Ohio is divided into 16 congressional districts, each represented by a member of the United States House of Representatives. After the 2010 Census, Ohio lost two House seats due to slow population growth compared to the national average, and a new map was signed into law on September 26, 2011. This map was ruled unconstitutional as partisan gerrymandering, and state Republicans were told to redraw the map before June 14, 2019. However, on October 7, 2019, the U.S. Supreme Court dismissed the challenge to the map, allowing it to stay in effect for the 2020 election.


title: Ohio's congressional districts

text: Starting in the 2022 midterms, per the 2020 United States census, Ohio will lose a congressional seat. On November 17, 2021, after lengthy discussions, a new map was passed by the Ohio House of Representatives 55-36, along party lines, with no Democrat voting in favor of the map. The map was sent to Governor of Ohio, Mike DeWine, where he accepted it 3 days later on November 20th.


title: Ohio's congressional districts

text: The map has been controversial, as Democrats accuse the map of being purposefully designed to benefit Republicans. By December 7, 2021, six lawsuits had been filed against the new 15-seat congressional map, citing it as "racially discriminatory". The proposed map favors Republican to Democratic districts by a 12-3 margin.


title: Ohio's congressional districts

text: On January 14, 2022, the Ohio Supreme Court declared the map a partisan gerrymander, violating Article XIX of the Constitution of Ohio, in a 4-3 decision. The Ohio General Assembly had 30 days to draw a new map.


title: Ohio's congressional districts

text: On March 16, 2022, the Ohio Supreme Court rejected the new proposed state legislative district map for the third time. The decision will most likely force Ohio to postpone its primary elections, scheduled to take place on May 3, until new maps of both state legislative seats and districts for the United States House of Representatives pass constitutional muster.


title: Ohio's congressional districts

text: On May 3, 2019, a three-judge panel from the United States District Court for the Southern District of Ohio declared the Ohio's 2012 district map contrary to Article One of the United States Constitution, as "an unconstitutional partisan gerrymander" and ordered "the enactment of a constitutionally viable replacement" prior to the 2020 elections. An appeal made to the U.S. Supreme Court resulted in the order to redraw the map being nullified.


title: Ohio's congressional districts

text: The following table is a list of members of the Ohio United States House delegation, their terms, their district boundaries, and the districts' political rating according to the CPVI. The delegation has a total of 16 members, with 12 Republicans and 4 Democrats.


title: Isotopes of helium

text: Although there are nine known isotopes of helium (He) (standard atomic weight: ), only helium-3 () and helium-4 () are stable. All radioisotopes are short-lived, the longest-lived being with a half-life of . The least stable is , with a half-life of (), although it is possible that may have an even shorter half-life.


title: Isotopes of helium

text: In the Earth's atmosphere, the ratio of to is . However, the isotopic abundance of helium varies greatly depending on its origin. In the Local Interstellar Cloud, the proportion of to is , which is times higher than that of atmospheric helium. Rocks from the Earth's crust have isotope ratios varying by as much as a factor of ten; this is used in geology to investigate the origin of rocks and the composition of the Earth's mantle. The different formation processes of the two stable isotopes of helium produce the differing isotope abundances.


title: Isotopes of helium

text: Equal mixtures of liquid and below separate into two immiscible phases due to differences in quantum statistics: atoms are bosons while atoms are fermions. Dilution refrigerators take advantage of the immiscibility of these two isotopes to achieve temperatures of a few millikelvins.


title: Isotopes of helium

text: Helium-2 or is an extremely unstable isotope of helium. Its nucleus, a diproton, consists of two protons with no neutrons. According to theoretical calculations, it would have been much more stable (although still undergoing β decay to deuterium) if the strong interaction had been 2% greater. Its instability is due to spin–spin interactions in the nuclear force, and the Pauli exclusion principle, which forces the two protons to have anti-aligned spins and gives the diproton a negative binding energy.


title: Isotopes of helium

text: There may have been observations of . In 2000, physicists first observed a new type of radioactive decay in which a nucleus emits two protons at once—perhaps a nucleus. The team led by Alfredo Galindo-Uribarri of the Oak Ridge National Laboratory announced that the discovery will help scientists understand the strong nuclear force and provide fresh insights into the creation of elements inside stars. Galindo-Uribarri and co-workers chose an isotope of neon with an energy structure that prevents it from emitting protons one at a time. This means that the two protons are ejected simultaneously. The team fired a beam of fluorine ions at a proton-rich target to produce , which then decayed into oxygen and two protons. Any protons ejected from the target itself were identified by their characteristic energies. There are two ways in which the two-proton emission may proceed. The neon nucleus might eject a "diproton"—a pair of protons bundled together as a nucleus—which then decays into separate protons. Alternatively, the protons may be emitted separately but simultaneously—so-called "democratic decay". The experiment was not sensitive enough to establish which of these two processes was taking place.


title: Isotopes of helium

text: More evidence of was found in 2008 at the Istituto Nazionale di Fisica Nucleare, in Italy. A beam of ions was directed at a target of beryllium foil. This collision converted some of the heavier neon nuclei in the beam into nuclei. These nuclei then collided with a foil of lead. The second collision had the effect of exciting the nucleus into a highly unstable condition. As in the earlier experiment at Oak Ridge, the nucleus decayed into an nucleus, plus two protons detected exiting from the same direction. The new experiment showed that the two protons were initially ejected together, correlated in a quasibound S configuration, before decaying into separate protons much less than a nanosecond later.


title: Isotopes of helium

text: Further evidence comes from RIKEN in Japan and the Joint Institute for Nuclear Research in Dubna, Russia, where beams of nuclei were directed at a cryogenic hydrogen target to produce . It was discovered that the nucleus can donate all four of its neutrons to the hydrogen. The two remaining protons could be simultaneously ejected from the target as a nucleus, which quickly decayed into two protons. A similar reaction has also been observed from nuclei colliding with hydrogen.


title: Isotopes of helium

text: The hypothetical effect of the binding of the diproton on Big Bang and stellar nucleosynthesis has been investigated. Some models suggest that variations in the strong force allowing the existence of a bound diproton would enable the conversion of all primordial hydrogen to helium in the Big Bang, with catastrophic consequences on the development of stars and life. This proposition is used as an example of the anthropic principle. However, a 2009 study suggests that such a conclusion cannot be drawn, as the formed diprotons would still decay to deuterium, whose binding energy would also increase. In some scenarios, it is postulated that hydrogen (in the form of deuterium) could still survive in relatively large quantities, rebutting arguments that the strong force is tuned within a precise anthropic limit.


title: Isotopes of helium

text: is stable and is the only stable isotope other than with more protons than neutrons. (There are many such unstable isotopes, the lightest being and .) There is only a trace amount () of on Earth, primarily present since the formation of the Earth, although some falls to Earth trapped in cosmic dust. Trace amounts are also produced by the beta decay of tritium. In stars, however, is more abundant, a product of nuclear fusion. Extraplanetary material, such as lunar and asteroid regolith, has trace amounts of from solar wind bombardment.


title: Isotopes of helium

text: For helium-3 to form a superfluid, it must be cooled to a temperature of , or almost a thousand times lower than helium-4 (). This difference is explained by quantum statistics, since helium-3 atoms are fermions, while helium-4 atoms are bosons, which condense to a superfluid more easily.


title: Isotopes of helium

text: The most common isotope, , is produced on Earth by alpha decay of heavier radioactive elements; the alpha particles that emerge are fully ionized nuclei. is an unusually stable nucleus because its nucleons are arranged into complete shells. It was also formed in enormous quantities during Big Bang nucleosynthesis.


title: Isotopes of helium

text: Terrestrial helium consists almost exclusively () of this isotope. Helium-4's boiling point of is the second lowest of all known substances, second only to helium-3. When cooled further to , it transforms to a unique superfluid state of zero viscosity. It solidifies only at pressures above 25 atmospheres, where its melting point is .


title: Isotopes of helium

text: Although all heavier helium isotopes decay with a half-life of less than one second, researchers have used particle accelerator collisions to create unusual atomic nuclei for elements such as helium, lithium and nitrogen. The unusual nuclear structures of such isotopes may offer insight into the isolated properties of neutrons.


title: Isotopes of helium

text: The shortest-lived isotope is helium-10 with a half-life of . Helium-6 decays by emitting a beta particle and has a half-life of . The most widely studied heavy helium isotope is helium-8. This isotope, as well as helium-6, is thought to consist of a normal helium-4 nucleus surrounded by a neutron "halo" (containing two neutrons in and four neutrons in ). Halo nuclei have become an area of intense research. Isotopes up to helium-10, with two protons and eight neutrons, have been confirmed. , despite being a doubly magic isotope, has a very short half-life; it is not particle-bound and near-instantaneously drips out two neutrons.


title: Aldol reaction

text: Discovered independently by the Russian chemist Alexander Borodin in 1869 and by the French chemist Charles-Adolphe Wurtz in 1872, the reaction combines two carbonyl compounds (the original experiments used aldehydes) to form a new β-hydroxy carbonyl compound. These products are known as "aldols", from the "ald"ehyde + alcoh"ol", a structural motif seen in many of the products. Aldol structural units are found in many important molecules, whether naturally occurring or synthetic.


title: Aldol reaction

text: For example, the aldol reaction has been used in the large-scale production of the commodity chemical pentaerythritol


title: Aldol reaction

text: The aldol reaction unites two relatively simple molecules into a more complex one. Increased complexity arises because up to two new stereogenic centers (on the α- and β-carbon of the aldol adduct, marked with asterisks in the scheme below) are formed. Modern methodology is capable of not only allowing aldol reactions to proceed in high yield but also controlling both the relative and absolute configuration of these stereocenters. This ability to selectively synthesize a particular stereoisomer is significant because stereoisomers can have distinctive chemical and biological properties.


title: Aldol reaction

text: For example, stereogenic aldol units are especially common in polyketides, a class of molecules found in biological organisms. In nature, polyketides are synthesized by enzymes that effect iterative Claisen condensations. The 1,3-dicarbonyl products of these reactions can then be variously derivatized to produce a wide variety of interesting structures. Often, such derivitization involves the reduction of one of the carbonyl groups, producing the aldol subunit. Some of these structures have potent biological properties: the immunosuppressant FK506, the anti-tumor agent discodermolide, or the antifungal agent amphotericin B, for example. Although the synthesis of many such compounds was once considered nearly impossible, aldol methodology has allowed their efficient synthesis in many cases.


title: Aldol reaction

text: A typical modern aldol addition reaction, shown above, might involve the nucleophilic addition of a ketone enolate to an aldehyde. Once formed, the aldol product can sometimes lose a molecule of water to form an α,β-unsaturated carbonyl compound. This is called "aldol condensation". A variety of nucleophiles may be employed in the aldol reaction, including the enols, enolates, and enol ethers of ketones, aldehydes, and many other carbonyl compounds. The electrophilic partner is usually an aldehyde or ketone (many variations, such as the Mannich reaction, exist). When the nucleophile and electrophile are different, the reaction is called a "crossed aldol reaction"; on the converse, when the nucleophile and electrophile are the same, the reaction is called an "aldol dimerization".


title: Aldol reaction

text: The aldol reaction may proceed by two distinct mechanisms. Carbonyl compounds, such as aldehydes and ketones, can be converted to enols or enol ethers. These species, being nucleophilic at the α-carbon, can attack especially reactive protonated carbonyls such as protonated aldehydes. This is the 'enol mechanism'. Carbonyl compounds, being carbon acids, can also be deprotonated to form enolates, which are much more nucleophilic than enols or enol ethers and can attack electrophiles directly. The usual electrophile is an aldehyde, since ketones are much less reactive. This is the 'enolate mechanism'.


title: Aldol reaction

text: Despite the attractiveness of the aldol manifold, there are several problems that need to be addressed to render the process catalytic and effective. The first problem is a thermodynamic one: most aldol reactions are reversible. Furthermore, the equilibrium is also just barely on the side of the products in the case of simple aldehyde–ketone aldol reactions. If the conditions are particularly harsh (e.g.: NaOMe/MeOH/reflux), condensation may occur, but this can usually be avoided with mild reagents and low temperatures (e.g., LDA (a strong base), THF, −78 °C). Although the aldol addition usually proceeds to near completion under irreversible conditions, the isolated aldol adducts are sensitive to base-induced retro-aldol cleavage to return starting materials. In contrast, retro-aldol condensations are rare, but possible. This is the basis of the catalytic strategy of class I aldolases in nature, as well as numerous small-molecule amine catalysts.


title: Aldol reaction

text: When an acid catalyst is used, the initial step in the reaction mechanism involves acid-catalyzed tautomerization of the carbonyl compound to the enol. The acid also serves to activate the carbonyl group of "another molecule" by protonation, rendering it highly electrophilic. The enol is nucleophilic at the α-carbon, allowing it to attack the protonated carbonyl compound, leading to the aldol after deprotonation. This usually dehydrates to give the unsaturated carbonyl compound. The scheme shows a typical acid-catalyzed self-condensation of an aldehyde.


title: Aldol reaction

text: If the catalyst is a moderate base such as hydroxide ion or an alkoxide, the aldol reaction occurs via nucleophilic attack by the resonance-stabilized enolate on the carbonyl group of another molecule. The product is the alkoxide salt of the aldol product. The aldol itself is then formed, and it may then undergo dehydration to give the unsaturated carbonyl compound. The scheme shows a simple mechanism for the base-catalyzed aldol reaction of an aldehyde with itself.


title: Aldol reaction

text: Base-catalyzed dehydration (frequently written incorrectly as a single step, see E1cB elimination reaction)


title: Aldol reaction

text: Although only a catalytic amount of base is required in some cases, the more usual procedure is to use a stoichiometric amount of a strong base such as LDA or NaHMDS. In this case, enolate formation is irreversible, and the aldol product is not formed until the metal alkoxide of the aldol product is protonated in a separate workup step.


title: Aldol reaction

text: More refined forms of the mechanism are known. In 1957, Howard Zimmerman and Marjorie D. Traxler proposed that some aldol reactions have "six-membered transition states having a chair conformation." This is now known as the Zimmerman–Traxler model. "E"-enolates give rise to anti products, whereas "Z"-enolates give rise to syn products. The factors that control selectivity are the preference for placing substituents equatorially in six-membered transition states and the avoidance of syn-pentane interactions, respectively. E and Z refer to the cis-trans stereochemical relationship between the enolate oxygen bearing the positive counterion and the highest priority group on the alpha carbon. In reality, only some metals such as lithium reliably follow the Zimmerman–Traxler model. Thus, in some cases, the stereochemical outcome of the reaction may be unpredictable.


title: Aldol reaction

text: The problem of "control" in the aldol addition is best demonstrated by an example. Consider the outcome of this hypothetical reaction:


title: Aldol reaction

text: In this reaction, two unsymmetrical ketones are being condensed using sodium ethoxide. The basicity of sodium ethoxide is such that it cannot fully deprotonate either of the ketones, but can produce small amounts of the sodium enolate of both ketones. This means that, in addition to being potential aldol electrophiles, both ketones may also act as nucleophiles via their sodium enolate. Two electrophiles and two nucleophiles, then, have potential to result in four possible products:


title: Aldol reaction

text: Thus, if one wishes to obtain only one of the cross-products, one must control which carbonyl becomes the nucleophilic enol/enolate and which remains in its electrophilic carbonyl form.


title: Aldol reaction

text: The simplest control is if only one of the reactants has acidic protons, and only this molecule forms the enolate. For example, the addition of diethyl malonate into benzaldehyde would produce only one product. Only the malonate has α hydrogens, so it is the nucleophilic partner, whereas the non-enolizeable benzaldehyde can only be the electrophile:


title: Aldol reaction

text: The malonate is particularly easy to deprotonate because the α position is flanked by more than one carbonyl. Double-activation makes the enolate more stable, so not as strong a base is required to form it. An extension of this effect can allow control over which of the two carbonyl reactants becomes the enolate even if both do have α hydrogens. If one partner is considerably more acidic than the other, the most acidic proton is abstracted by the base and an enolate is formed at that carbonyl while the carbonyl that is less acidic is not affected by the base. This type of control works only if the difference in acidity is large enough and no excess of base is used for the reaction. A typical substrate for this situation is when the deprotonatable position is activated by more than one carbonyl-like group. Common examples include a CH group flanked by two carbonyls or nitriles (see for example the Knoevenagel condensation and the first steps of the malonic ester synthesis and acetoacetic ester synthesis).


title: Aldol reaction

text: One common solution is to form the enolate of one partner first, and then add the other partner under kinetic control. Kinetic control means that the forward aldol addition reaction must be significantly faster than the reverse retro-aldol reaction. For this approach to succeed, two other conditions must also be satisfied; it must be possible to quantitatively form the enolate of one partner, and the forward aldol reaction must be significantly faster than the transfer of the enolate from one partner to another. Common kinetic control conditions involve the formation of the enolate of a ketone with LDA at −78 °C, followed by the slow addition of an aldehyde.


title: Aldol reaction

text: The enolate may be formed by using a strong base ("hard conditions", pathway 1 below) or using a Lewis acid and a weak base ("soft conditions", pathway 2 below):


title: Aldol reaction

text: For deprotonation to occur, the stereoelectronic requirement is that the alpha-C-H sigma bond must be able to overlap with the pi* orbital of the carbonyl:


title: Aldol reaction

text: Extensive studies have been performed on the formation of enolates. It is possible to generate, in most cases, the desired enolate geometry:


title: Aldol reaction

text: For ketones, most enolization conditions give "Z" enolates. For esters, most enolization conditions give "E" enolates. The addition of HMPA is known to reverse the stereoselectivity of deprotonation.


title: Aldol reaction

text: The stereoselective formation of enolates has been rationalized with the Ireland model, although its validity is somewhat questionable. In most cases, it is not known which, if any, intermediates are monomeric or oligomeric in nature; nonetheless, the Ireland model remains a useful tool for understanding enolates.


title: Aldol reaction

text: In the Ireland model, the deprotonation is assumed to proceed by a six-membered or cyclic monomeric transition state. The larger of the two substituents on the electrophile (in the case above, methyl is larger than proton) adopts an equatorial disposition in the favored transition state, leading to a preference for E enolates. The model clearly fails in many cases; for example, if the solvent mixture is changed from THF to 23% HMPA-THF (as seen above), the enolate geometry is reversed, which is inconsistent with this model and its cyclic transition state.


title: Aldol reaction

text: If an unsymmetrical ketone is subjected to base, it has the potential to form two regioisomeric enolates (ignoring enolate geometry). For example:


title: Aldol reaction

text: The trisubstituted enolate is considered the kinetic enolate, while the tetrasubstituted enolate is considered the thermodynamic enolate. The alpha hydrogen deprotonated to form the kinetic enolate is less hindered, and therefore deprotonated more quickly. In general, tetrasubstituted olefins are more stable than trisubstituted olefins due to hyperconjugative stabilization. The ratio of enolate regioisomers is heavily influenced by the choice of base. For the above example, kinetic control may be established with LDA at −78 °C, giving 99:1 selectivity of kinetic: thermodynamic enolate, while thermodynamic control may be established with triphenylmethyllithium at room temperature, giving 10:90 selectivity.


title: Aldol reaction

text: In general, kinetic enolates are favored by cold temperatures, conditions that give relatively ionic metal–oxygen bonding, and rapid deprotonation using a slight excess of a strong, sterically hindered base. The large base only deprotonates the more accessible hydrogen, and the low temperatures and excess base help avoid equilibration to the more stable alternate enolate after initial enolate formation. Thermodynamic enolates are favored by longer equilibration times at higher temperatures, conditions that give relatively covalent metal–oxygen bonding, and use of a slight sub-stoichiometric amount of strong base. By using insufficient base to deprotonate all of the carbonyl molecules, the enolates and carbonyls can exchange protons with each other and equilibrate to their more stable isomer. Using various metals and solvents can provide control over the amount of ionic character in the metal–oxygen bond.


title: Aldol reaction

text: The aldol reaction is particularly useful because two new stereogenic centers are generated in one reaction. The "syn"/"anti" convention is commonly used to denote the relative stereochemistry at the α- and β-carbon.


title: Aldol reaction

text: The convention applies when propionate (or higher order) nucleophiles are added to aldehydes. The "R" group of the ketone and the "R"' group of the aldehyde are aligned in a "zig zag" pattern in the plane of the paper (or screen), and the disposition of the formed stereocenters is deemed "syn" or "anti", depending if they are on the same or opposite sides of the main chain.


title: Aldol reaction

text: There is no significant difference between the level of stereoinduction observed with "E" and "Z" enolates. Each alkene geometry leads primarily to one specific relative stereochemistry in the product, "E" giving "anti" and "Z" giving "syn":


title: Aldol reaction

text: The enolate metal cation may play a large role in determining the level of stereoselectivity in the aldol reaction. Boron is often used because its bond lengths are significantly shorter than that of metals such as lithium, aluminium, or magnesium.


title: Aldol reaction

text: For example, boron–carbon and boron–oxygen bonds are 1.4–1.5 Å and 1.5–1.6 Å in length, respectively, whereas typical metal-carbon and metal-oxygen bonds are 1.9–2.2 Å and 2.0–2.2 Å in length, respectively. The use of boron rather than a metal "tightens" the transition state and gives greater stereoselectivity in the reaction. Thus the above reaction gives a "syn:anti" ratio of 80:20 using a lithium enolate compared to 97:3 using a bibutylboron enolate.


title: Aldol reaction

text: The aldol reaction may exhibit "substrate-based stereocontrol", in which existing chirality on either reactant influences the stereochemical outcome of the reaction. This has been extensively studied, and in many cases, one can predict the sense of asymmetric induction, if not the absolute level of diastereoselectivity. If the enolate contains a stereocenter in the alpha position, excellent stereocontrol may be realized.


title: Aldol reaction

text: In the case of an E enolate, the dominant control element is allylic 1,3-strain whereas in the case of a Z enolate, the dominant control element is the avoidance of 1,3-diaxial interactions. The general model is presented below:


title: Aldol reaction

text: For clarity, the stereocenter on the enolate has been epimerized; in reality, the opposite diastereoface of the aldehyde would have been attacked. In both cases, the 1,3-syn diastereomer is favored. There are many examples of this type of stereocontrol:


title: Aldol reaction

text: When enolates attacks aldehydes with an alpha stereocenter, excellent stereocontrol is also possible. The general observation is that "E" enolates exhibit Felkin diastereoface selection, while "Z" enolates exhibit anti-Felkin selectivity. The general model is presented below:


title: Aldol reaction

text: Since "Z" enolates must react through a transition state that contains either a destabilizing syn-pentane interaction or an anti-Felkin rotamer, "Z"-enolates exhibit lower levels of diastereoselectivity in this case. Some examples are presented below:


title: Aldol reaction

text: If both the enolate and the aldehyde contain pre-existing chirality, then the outcome of the "double stereodifferentiating" aldol reaction may be predicted using a merged stereochemical model that takes into account the enolate facial bias, enolate geometry, and aldehyde facial bias. Several examples of the application of this model are given below:


title: Aldol reaction

text: A widely used method is the Evans' acyl oxazolidinone method. Developed in the late 1970s and 1980s by David A. Evans and coworkers, the method works by temporarily creating a chiral enolate by appending a chiral auxiliary. The pre-existing chirality from the auxiliary is then transferred to the aldol adduct by performing a diastereoselective aldol reaction. Upon subsequent removal of the auxiliary, the desired aldol stereoisomer is revealed.


title: Aldol reaction

text: In the case of the Evans' method, the chiral auxiliary appended is an oxazolidinone, and the resulting carbonyl compound is an imide. A number of oxazolidinones are now readily available in both enantiomeric forms. They are relatively expensive. However, enantiopure oxazolidinones are derived in 2 synthetic steps from comparatively inexpensive amino acids, which means that large-scale syntheses can be made more economical by in-house preparation. This usually involves borohydride mediated reduction of the acid moiety, followed by condensation/cyclisation of the resulting amino alcohol with a simple carbonate ester such as diethylcarbonate.


title: Aldol reaction

text: The acylation of an oxazolidinone is a convenient procedure, and is informally referred to as "loading done". "Z"-enolates, leading to syn-aldol adducts, can be reliably formed using boron-mediated soft enolization:


title: Aldol reaction

text: Often, a single diastereomer may be obtained by one crystallization of the aldol adduct. However, anti-aldol adducts cannot be obtained reliably with the Evans method. Despite the cost and the limitation to give only "syn" adducts, the method's superior reliability, ease of use, and versatility render it the method of choice in many situations. Many methods are available for the cleavage of the auxiliary:


title: Aldol reaction

text: Upon construction of the imide, both syn- and anti-selective aldol addition reactions may be performed, allowing the assemblage of three of the four possible stereoarrays: syn selective: and anti selective:


title: Aldol reaction

text: In the syn-selective reactions, both enolization methods give the "Z" enolate, as expected; however, the stereochemical outcome of the reaction is controlled by the methyl stereocenter, rather than the chirality of the oxazolidinone. The methods described allow the stereoselective assembly of polyketides, a class of natural products that often feature the aldol retron.


title: Aldol reaction

text: Intramolecular aldol reaction is the condensation reaction of two aldehyde groups or ketone groups in the same molecule. Five- or six-membered , -unsaturated ketone or aldehydes are formed as products. This reaction is an important approach to the formation of carbon-carbon bonds in organic molecules containing ring systems. As an example, under strong basic conditions (e.g. sodium hydroxide), hexane-2,5-dione (compound A in Figure 1) can cyclize via intramolecular aldol reaction to form the 3-methylcyclopent-2-en-1-one (compound B).


title: Aldol reaction

text: The mechanism of the intramolecular aldol reaction involves formation of a key enolate intermediate followed by an intramolecular nucleophilic addition process. First, hydroxide abstracts the α-hydrogen on a terminal carbon to form the enolate. Next, a nucleophilic attack of the enolate on the other keto group forms a new carbon-carbon bond (red) between carbons 2 and 6. At last, usually under heating conditions, the elimination of water molecule yields the cyclized α,β-unsaturated ketone.


title: Aldol reaction

text: Intramolecular aldol reactions have been widely used in total syntheses of various natural products, especially alkaloids and steroids. An example is the application of an intramolecular aldol reaction in the ring closure step for total synthesis of (+)-Wortmannin by Shigehisa, et al. (Figure 2).


title: Aldol reaction

text: A key limitation to the chiral auxiliary approach described previously is the failure of N-acetyl imides to react selectively. An early approach was to use a temporary thioether group:


title: Aldol reaction

text: The Mukaiyama aldol reaction is the nucleophilic addition of silyl enol ethers to aldehydes catalyzed by a Lewis acid such as boron trifluoride (as boron trifluoride etherate) or titanium tetrachloride. The Mukaiyama aldol reaction does not follow the Zimmerman-Traxler model. Carreira has described particularly useful asymmetric methodology with silyl ketene acetals, noteworthy for its high levels of enantioselectivity and wide substrate scope.


title: Aldol reaction

text: The method works on unbranched aliphatic aldehydes, which are often poor electrophiles for catalytic, asymmetric processes. This may be due to poor electronic and steric differentiation between their enantiofaces.


title: Aldol reaction

text: The analogous vinylogous Mukaiyama aldol process can also be rendered catalytic and asymmetric. The example shown below works efficiently for aromatic (but not aliphatic) aldehydes and the mechanism is believed to involve a chiral, metal-bound dienolate.


title: Aldol reaction

text: a thiazolidinethione performs acetate aldol reactions. and can produce the "Evans syn" or "non-Evans syn" adducts by simply varying the amount of (−)-sparteine. The reaction is believed to proceed via six-membered, titanium-bound transition states, analogous to the proposed transition states for the Evans auxiliary. NOTE: the structure of sparteine shown below is missing a N atom.


title: Aldol reaction

text: Chiral secondary amine catalysts catalyze some aldol reactions. These secondary amines form transient enamines when exposed to ketones, which may react enantioselectively with suitable aldehyde electrophiles. The amine reacts with the carbonyl to form an enamine, the enamine acts as an enol-like nucleophile, and then the amine is released from the product all—the amine itself is a catalyst. This enamine catalysis method is a type of organocatalysis, since the catalyst is entirely based on a small organic molecule. In a seminal example, proline efficiently catalyzed the cyclization of a triketone:


title: Aldol reaction

text: This reaction is known as the Hajos-Parrish reaction (also known as the Hajos-Parrish-Eder-Sauer-Wiechert reaction, referring to a contemporaneous report from Schering of the reaction under harsher conditions). Under the Hajos-Parrish conditions only a catalytic amount of proline is necessary (3 mol%). There is no danger of an achiral background reaction because the transient enamine intermediates are much more nucleophilic than their parent ketone enols. This strategy offers a simple way of generating enantioselectivity in reactions without using transition metals, which have the possible disadvantages of being toxic or expensive.


title: Aldol reaction

text: Proline-catalyzed aldol reactions do not show any non-linear effects (the enantioselectivity of the products is directly proportional to the enantiopurity of the catalyst). Combined with isotopic labelling evidence and computational studies, the proposed reaction mechanism for proline-catalyzed aldol reactions is as follows: