Radical-based asymmetric synthesis: an iterative approach to 1, 3, 5, ... (2n + 1) polyols

[formula: see text] A conceptually novel approach to 1, 3, 5, ... (2n + 1) polyols based on iterative stereo-controlled homologation of chiral hydroxyalkyl radicals is reported. Starting from alpha-keto ester precursors, the general sequence of (1) ketone reduction, (2) auxiliary attachment, (3) saponification, (4) Barton esterification, and (5) radical addition provided the two-carbon homologue in 70-80% overall yield. The simplicity and generality of this iterative strategy for 1, 3, 5, ... (2n + 1) polyol synthesis suggests an attractive alternative for the preparation of molecules containing this structural motif.