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Updated: Jan 4, 2026

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species
Published on: August 16, 2018
Manganese-Catalyzed Stereospecific Hydroxymethylation of Alkyl Tosylates
Hannah Shenouda1, Erik J Alexanian1
1Department of Chemistry , The University of North Carolina at Chapel Hill , Chapel Hill , North Carolina 27599 , United States.
Abstract:
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.
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