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Bicyclopentylation of Alcohols with Thianthrenium Reagents.

ABSTRACT: Herein we present the first method for the synthesis of bicyclo[1.1.1]pentyl (BCP) alkyl ethers from alcohols. The reaction uses BCP-thianthrenium reagents and is catalyzed by a dual copper/photoredox catalyst system. Unlike known alkylations of tertiary alcohols via carbocation intermediates, our Cu-mediated radical process circumvents the labile BCP carbocations. The approach demonstrates a broad tolerance for functional groups when applied to primary, secondary, and even tertiary alcohols. In addition, we highlight the utility of this method in late-stage functionalizations of both natural products and pharmaceuticals as well as in the rapid construction of BCP analogs of known pharmaceuticals that would otherwise be difficult to access.

SUBMITTER: Bai Z

PROVIDER: S-EPMC10704608 | biostudies-literature | 2023 Dec

REPOSITORIES: biostudies-literature

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Bicyclopentylation of Alcohols with Thianthrenium Reagents.

Bai Zibo Z Lansbergen Beatrice B Ritter Tobias T

Journal of the American Chemical Society 20231127 48

Herein we present the first method for the synthesis of bicyclo[1.1.1]pentyl (BCP) alkyl ethers from alcohols. The reaction uses BCP-thianthrenium reagents and is catalyzed by a dual copper/photoredox catalyst system. Unlike known alkylations of tertiary alcohols via carbocation intermediates, our Cu-mediated radical process circumvents the labile BCP carbocations. The approach demonstrates a broad tolerance for functional groups when applied to primary, secondary, and even tertiary alcohols. In ...[more]

PMID: 38010346

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