Stereoselective reactions, 25. Enantioselective deprotonation of prochiral 4-substituted cyclohexanones by chiral chelated lithium amides

Article abstract of DOI:10.1016/S0040-4020(97)00288-3

Enantioselective deprotonation of prochiral 4-substituted cyclohexanones (4a-d) by chiral chelated lithium amides (8a-k) in the presence of excess trimethylsilyl chloride was realized to give the corresponding chiral silyl enol ethers (6a-d) in up to 89% ee. It is shown that enantioselectivity of the reaction is dependent on the solvent used, but becomes almost independent on the solvent in the presence of HMPA. The sense of asymmetric induction can be correlated to the configuration at the chiral carbon bearing amide nitrogen of the lithium amide.