Copper-Catalyzed Regiodivergent Internal Allylic Alkylations

Madhu Sudan Manna; Seok Yeol Yoo; Mohammed Sharique; Hyoju Choi; Bimal Pudasaini; Mu Hyun Baik; Uttam K. Tambar

doi:10.1002/anie.202304848

Copper-Catalyzed Regiodivergent Internal Allylic Alkylations

Madhu Sudan Manna, Seok Yeol Yoo, Mohammed Sharique, Hyoju Choi, Bimal Pudasaini, Mu Hyun Baik, Uttam K. Tambar

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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_N2 or S_N2′ 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.

Original language	English (US)
Article number	e202304848
Journal	Angewandte Chemie - International Edition
Volume	62
Issue number	35
DOIs	https://doi.org/10.1002/anie.202304848
State	Published - Aug 28 2023

Keywords

Allylic Alkylation
Copper
Density Functional Calculations
Regioselecitvity
Stereospecific

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1002/anie.202304848

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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 SN2 or SN2′ 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.",

keywords = "Allylic Alkylation, Copper, Density Functional Calculations, Regioselecitvity, Stereospecific",

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T1 - Copper-Catalyzed Regiodivergent Internal Allylic Alkylations

AU - Manna, Madhu Sudan

AU - Yoo, Seok Yeol

AU - Sharique, Mohammed

AU - Choi, Hyoju

AU - Pudasaini, Bimal

AU - Baik, Mu Hyun

AU - Tambar, Uttam K.

PY - 2023/8/28

Y1 - 2023/8/28

N2 - 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 SN2 or SN2′ 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.

AB - 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 SN2 or SN2′ 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.

KW - Allylic Alkylation

KW - Copper

KW - Density Functional Calculations

KW - Regioselecitvity

KW - Stereospecific

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Copper-Catalyzed Regiodivergent Internal Allylic Alkylations

Abstract

Keywords

ASJC Scopus subject areas

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