Manganese-Catalyzed Stereospecific Hydroxymethylation of Alkyl Tosylates.

The development of a stereospecific hydroxymethylation of alkyl tosylates using an inexpensive, first-row catalyst is described. The transformation proceeds under mild conditions with low pressure to deliver homologated alcohols as products. Chiral, nonracemic β-branched primary alcohols are obtained with high enantiospecificity from easily accessed secondary alkyl substrates. Simple modification of the reaction system also permits access to α-d2 alcohols. These studies use anionic metal carbonyl catalysis to access a synthetic equivalent of the challenging hydroxymethyl anion from carbon monoxide.