Absolute Autocatalytic Amplification under Heterogenous Phase Conditions Involving Subsequent Hydride Transfer and a Hemiacetal Intermediate

Abstract

Abstract: In contrast to the homogenous phase, absolute asymmetric amplification of pyridine alkanol is observed under heterogenous conditions. The reaction of iPr2Zn vapor on a solid powder of pyridine carbaldehyde induced autocatalytic amplification of chirality providing the alkanol product with an enantiopurity up to 90 % ee. In this study, side products were identified and their formation is traced back to redox pathways involving hydride transfer, namely a chiral ester resulting most probably from a disproportionation of the starting aldehyde into a hemiacetal and subsequent hydride loss following a Claisen-Tishchenko mechanism. These observations provide new perspectives in the elucidation of the mechanism of amplification of chirality in the Soai reaction.