Stereoselective Syntheses of Building Blocks with Three Consecutive Stereogenic Centers: Important Precursors of Polyketide Natural Products [New Synthetic Methods (68)]

Sequences of directly adjacent stereogenic centers were first discovered for the monosaccharides, which therefore constituted the first focus of interest in Stereoselective synthesis. The structures of many polyketide‐derived natural products that have been elucidated in recent years often exhibit longer sequences of stereogenic centers in which hydroxy‐substituted secondary carbon atoms alternate with tertiary carbon atoms. This finding inspired the development of methods allowing the specific construction of first two and then—more importantly–three neighboring stereogenic centers. The diverse methodologies that have thereby emerged reveal common principles and stress the variety of approaches possible in stereoselective synthesis.