Rhodium-Catalyzed Enantioselective Radical Addition of CX4 Reagents to Olefins

Bo Chen; Cheng Fang; Peng Liu; Joseph M. Ready

doi:10.1002/anie.201704074

Rhodium-Catalyzed Enantioselective Radical Addition of CX₄ Reagents to Olefins

Bo Chen, Cheng Fang, Peng Liu, Joseph M. Ready

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

67 Scopus citations

Abstract

We describe the synthetically useful enantioselective addition of Br−CX₃ (X=Cl or Br) to terminal olefins to introduce a trihalomethyl group and generate optically active secondary bromides. Computational and experimental evidence supports an asymmetric atom-transfer radical addition (ATRA) mechanism in which the stereodetermining step involves outer-sphere bromine abstraction from a [(bisphosphine)Rh^IIBrCl] complex by a benzylic radical intermediate. This mechanism appears unprecedented in asymmetric catalysis.

Original language	English (US)
Pages (from-to)	8780-8784
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	56
Issue number	30
DOIs	https://doi.org/10.1002/anie.201704074
State	Published - Jul 17 2017

Keywords

alkenes
asymmetric catalysis
enantioselectivity
radical reactions
rhodium

ASJC Scopus subject areas

Catalysis
General Chemistry

Access to Document

10.1002/anie.201704074

Cite this

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title = "Rhodium-Catalyzed Enantioselective Radical Addition of CX4 Reagents to Olefins",

abstract = "We describe the synthetically useful enantioselective addition of Br−CX3 (X=Cl or Br) to terminal olefins to introduce a trihalomethyl group and generate optically active secondary bromides. Computational and experimental evidence supports an asymmetric atom-transfer radical addition (ATRA) mechanism in which the stereodetermining step involves outer-sphere bromine abstraction from a [(bisphosphine)RhIIBrCl] complex by a benzylic radical intermediate. This mechanism appears unprecedented in asymmetric catalysis.",

keywords = "alkenes, asymmetric catalysis, enantioselectivity, radical reactions, rhodium",

author = "Bo Chen and Cheng Fang and Peng Liu and Ready, {Joseph M.}",

note = "Funding Information: Financial support was provided by the NIH (R01GM102403), the Welch Foundation (I-1612), and the University of Pittsburgh. DFT calculations were performed at the Center for Research Computing at the University of Pittsburgh and the Extreme Science and Engineering Discovery Environment (XSEDE) supported by the NSF. Publisher Copyright: {\textcopyright} 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

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AU - Chen, Bo

AU - Fang, Cheng

AU - Liu, Peng

AU - Ready, Joseph M.

N1 - Funding Information: Financial support was provided by the NIH (R01GM102403), the Welch Foundation (I-1612), and the University of Pittsburgh. DFT calculations were performed at the Center for Research Computing at the University of Pittsburgh and the Extreme Science and Engineering Discovery Environment (XSEDE) supported by the NSF. Publisher Copyright: © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2017/7/17

Y1 - 2017/7/17

N2 - We describe the synthetically useful enantioselective addition of Br−CX3 (X=Cl or Br) to terminal olefins to introduce a trihalomethyl group and generate optically active secondary bromides. Computational and experimental evidence supports an asymmetric atom-transfer radical addition (ATRA) mechanism in which the stereodetermining step involves outer-sphere bromine abstraction from a [(bisphosphine)RhIIBrCl] complex by a benzylic radical intermediate. This mechanism appears unprecedented in asymmetric catalysis.

AB - We describe the synthetically useful enantioselective addition of Br−CX3 (X=Cl or Br) to terminal olefins to introduce a trihalomethyl group and generate optically active secondary bromides. Computational and experimental evidence supports an asymmetric atom-transfer radical addition (ATRA) mechanism in which the stereodetermining step involves outer-sphere bromine abstraction from a [(bisphosphine)RhIIBrCl] complex by a benzylic radical intermediate. This mechanism appears unprecedented in asymmetric catalysis.

KW - alkenes

KW - asymmetric catalysis

KW - enantioselectivity

KW - radical reactions

KW - rhodium

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