Work

Synthesis of Highly Congested Tertiary Alcohols via the [3,3] Radical Deconstruction of Breslow Intermediates

Year: 2022

Type: article

Abstract: Pericyclic processes such as [3,3]-sigmatropic rearrangements leading to the rapid generation of molecular complexity constitute highly valuable tools in organic synthesis. Herein, we report the formation of particularly hindered tertiary alcohols via rearrangement of Breslow intermediates formed in situ from readily available N-allyl thiazolium salts and benzaldehyde derivatives. Experimental mechanistic studies performed suggest that the reaction proceeds via a close radical pair which recombine in a regio- and diastereoselective manner, formally leading to [3,3]-rearranged products.

Source: Organic Letters

DOI: 10.1021/acs.orglett.2c01627

Authors: Roger Machín Rivera, Nikolas R. Burton, Luke D. Call, Marshall A. Tomat, Vincent N. G. Lindsay

Institution: North Carolina State University

Language: English

Topic: Radical Photochemical Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: North Carolina State University, National Institutes of Health, National Institute of General Medical Sciences

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