Synthesis of the enantiomers of lasiol, an acyclic monoterpene alcohol in the mandibular gland secretion of the male ants, Lasius meridionalis.
(2S,3S)-(-)-Lasiol (2,3,6-trimethyl-5-hepten-1-ol, 1) and its antipode were synthesized from cis-4,5-dimethylcyclohexene oxide (3) by employing asymmetric cleavage of the epoxy ring with a chiral lithium amide derived from 4 to give optically active cis-4,5-dimethyl-2-cyclohexen-1-ol (5) as the key-step.
Lasiol, a new acyclic monoterpenol in the mandibular gland secretion of lasius meridionalis
Abstract A new, biogenetically anomalous, acyclic monoterpenol has been found in the mandibular glands of the formicine ant Lasius meridionalis , and identified as erythro - 1 , 2,3,6-trimethyl-5-heptenol (lasiol) on the basis of spectroscopic evidence and total synthesis.
Stereospecific Michael addition of dithioester enethiolates with acyclic enones
Abstract Cis lithium enethiolates, generated from substituted dithioesters, undergo 1,4-addition uith vapious β-monosubstituted α-unsaturated ketones. With acyclic enones one of the tw resulting diastereomeric 5-oxodithioesters is predominantly formed (ratio up to 95 : 5). Its anti configuration was proven by chemical correlation in one case. Evidence for fhe stereospecificity of this Michael, addition is given.