Zinc-Mediated Hydroxyallylation of Aldehydes with Cyclopropanols: Direct Access to Vicinal anti-sec,tert-Diols via Enolized Homoenolate

26 November 2021, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Direct and diastereoselective synthesis of vicinal anti-sec,tert-diols has been achieved by zinc-mediated α- hydroxyallylation of aldehydes with cyclopropanols. The reaction features the action of zinc enolized homoenolate, formed via ring opening of zinc cyclopropoxide and enolization of the resulting homoenolate, as γ-oxyallyl nucleophile toward the carbonyl electrophile, which stands in contrast to the previously described enolate mode of the same species. A bicyclic chairlike transition state wherein the aldehyde substituent favorably occupies the psuedoaxial position is proposed to account for the anti selectivity.

Keywords

C-C bond formation
allylation
organozinc compounds
aldehydes
cyclopropanols
diols

Supplementary materials

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Supporting Information
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Experimental procedures, characterization data for all the new compounds, and computational details.
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