Preparation of σ- and π-Allylcopper(III) Intermediates in S_N2 and S_N2' Reactions of Organocuprate(I) Reagents with Allylic Substrates

摘要

The reactions of organocopper(I) reagents with allylic substrates have been among their most valuable synthetic applications, and consequently, they have been scrutinized from experimental as well as theoretical3 points of view. Nevertheless, the outcome is difficult to predict for each new case, as the partition between S_N2 and S_N2' products is a complex function of the experimental parameters. Both σ- and π-allylcopper(III) intermediates have been proposed, and a detailed understanding of their roles can only accelerate progress in this important area, for example, in the development of enantioselective reactions.