Alexander V. Gontcharov

Studies on asymmetric conversion of arenes to functionalized cyclohexenones via chiral auxiliary-promoted nucleophilic additions to arene-chromium complexes

Abstract Reactions of alkoxyarene-chromium tricarbonyl complexes, having chiral alkoxy groups, with isobutyronitrile anion, followed by standard work-up produces substituted alkoxycyclohexadienes with diastereomeric excesses of up to 76%. Conversion to cyclohexenones allows recovery of the chiral alcohol auxiliary. The absolute stereochemistry of the product from the optimum procedure was determined by using Moshers method on the derived cyclohexenol.

CHIRAL AUXILIARY-PROMOTED ASYMMETRIC NUCLEOPHILE ADDITIONS TO ARENE-MANGANESE TRICARBONYL COMPLEXES

Abstract Addition of a range of nucleophiles to arene-manganese tricarbonyl complexes, carrying a chiral non-racemic 2,5-dimethylpyrrolidine substituent, results in diastereomeric excesses of up to 94%. Dependence of the level of asymmetric induction on reactivity and steric bulk of the nucleophile is observed, revealing a rather complex set of controlling factors for the reaction.