Axial-to-central chirality transfer in cyclization processes

Abstract

Substrates, bearing axial chirality, can cyclize intra- or inter-molecularly with concomitant transfer of axial-to-central chirality to produce at least one stereocenter. In order to satisfy a strict definition of axial-to-central chirality transfer, the initial axial chirality must be lost during the cyclization process. Highly functionalized enantiopure carbocycles and heterocycles were prepared using this strategy. The transformations of configurationally stable substrates take place with high regio- and stereo-selectivity. Selected examples involving allenes, biaryls, arylamides and transient axially chiral short-lived species are discussed. Special attention is focused on the mechanistic rationale of the chirality transfer.