Copper-Catalyzed Regiodivergent Internal Allylic Alkylations

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

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

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

Access to Document

10.1002/anie.202304848

Cite this

@article{bfff234564b84d7280d789d8ad938e4c,

title = "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 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",

author = "Manna, {Madhu S} and Yoo, {Seok Yeol} and Mohammed Sharique and Hyoju Choi and Bimal Pudasaini and Baik, {Mu Hyun} and Tambar, {Uttam K.}",

note = "Publisher Copyright: {\textcopyright} 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.",

year = "2023",

month = aug,

day = "28",

doi = "10.1002/anie.202304848",

language = "English (US)",

volume = "62",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley and Sons Ltd",

number = "35",

}

TY - JOUR

T1 - Copper-Catalyzed Regiodivergent Internal Allylic Alkylations

AU - Manna, Madhu S

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

UR - http://www.scopus.com/inward/record.url?scp=85164945554&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85164945554&partnerID=8YFLogxK

U2 - 10.1002/anie.202304848

DO - 10.1002/anie.202304848

M3 - Article

C2 - 37327025

AN - SCOPUS:85164945554

SN - 1433-7851

VL - 62

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 35

M1 - e202304848

ER -

Copper-Catalyzed Regiodivergent Internal Allylic Alkylations

Abstract

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this