α-Ketol and α-iminol rearrangements in synthetic organic and biosynthetic reactions (Beilstein Journal of Organic Chemistry)

Abstract In the presence of a suitable acid or base, α-hydroxyaldehydes, ketones, and imines can undergo isomerization that features the 1,2-shift of an alkyl or aryl group. In the process, the hydroxy group is converted to a carbonyl and the aldehyde/ketone or imine is converted to an alcohol or amine. Such α-ketol/α-iminol rearrangements are used in a wide variety of synthetic applications including asymmetric synthesis, tandem reactions, and the total synthesis and biosynthesis of natural products. This review explores the use of α-ketol rearrangements in these contexts over the past two decades. Beilstein J. Org. Chem. 2021, 17, 2570–2584. doi:10.3762/bjoc.17.172