A HIGH YIELDING, REPRODUCIBLE SYNTHESIS OF TRIMETHYLSILYLKETENE
ABSTRACT A two-step sequence for the preparation of trimethylsilylketene, from chloroacetaldehyde diethyl acetal via ethoxyacetylene, has been modified and optimized.
Carbonyl Homologation via β-Trimethylsilyl β-Lactone Rearrangements. A Nonbasic Alternative to the Wittig Reaction
Abstract Saturated and unsaturated aldehydes and ketones, when treated with trimethylsilylketene and BF3 for 16 hours, form β-lactones which spontaneously rearrange to α,β-unsaturated TMS esters; these hydrolyze during workup to form the corresponding carboxylic acids.
Highly enantio- and diastereoselective synthesis of β-methyl-γ-monofluoromethyl-substituted alcohols.
Enanatiopure β-methyl-γ-monofluoromethyl alcohols were prepared from the allylic alkylation between fluorobis(phenylsulfonyl)methane with Morita-Baylis-Hillman carbonates. The reaction was catalyzed by using the Cinchona alkaloid derivative, (DHQD)(2)AQN. The origin of the stereoselectivity was verified by DFT methods. Calculated geometries and relative energies of various transition states strongly support the observed stereoselectivity.