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. 2019 Nov 15;21(22):9268-9271.
doi: 10.1021/acs.orglett.9b03706. Epub 2019 Nov 5.

Manganese-Catalyzed Stereospecific Hydroxymethylation of Alkyl Tosylates

Hannah Shenouda  1 , Erik J Alexanian  1
Affiliations

Manganese-Catalyzed Stereospecific Hydroxymethylation of Alkyl Tosylates

Hannah Shenouda et al. Org Lett. .

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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Figures

Figure 1.
Figure 1.
Hydroxymethylations of alkyl electrophiles.
Scheme 1.
Scheme 1.
Plausible catalytic cycle for the stereospecific hydroxymethylation.
See this image and copyright information in PMC

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