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Copper-Catalyzed Regiodivergent Internal Allylic Alkylations.

ABSTRACT: We report a copper-catalyzed, regioselective, and stereospecific alkylation of unbiased internal allylic carbonates with functionalized alkyl and aryl Grignard reagents. The reactions exhibit high stereospecificity and regioselectivity for either S_N 2 or S_N 2' products under two sets of copper-catalyzed conditions, which enables the preparation of a broad range of products with E-alkene selectivity. Density functional theory calculations reveal the origins of the regioselectivity based on the different behaviors of homo- and heterocuprates.

SUBMITTER: Manna MS

PROVIDER: S-EPMC10528884 | biostudies-literature | 2023 Aug

REPOSITORIES: biostudies-literature

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Copper-Catalyzed Regiodivergent Internal Allylic Alkylations.

Manna Madhu Sudan MS Yoo Seok Yeol SY Sharique Mohammed M Choi Hyoju H Pudasaini Bimal B Baik Mu-Hyun MH Tambar Uttam K UK

Angewandte Chemie (International ed. in English) 20230717 35

We report a copper-catalyzed, regioselective, and stereospecific alkylation of unbiased internal allylic carbonates with functionalized alkyl and aryl Grignard reagents. The reactions exhibit high stereospecificity and regioselectivity for either SN 2 or SN 2' products under two sets of copper-catalyzed conditions, which enables the preparation of a broad range of products with E-alkene selectivity. Density functional theory calculations reveal the origins of the regioselec ...[more]

PMID: 37327025

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