Free-Radical Deoxygenative Amination of Alcohols via Copper Metallaphotoredox Catalysis

William P. Carson; Artem V. Tsymbal; Robert W. Pipal; Grant A. Edwards; Joseph R. Martinelli; Albert Cabré; David W.C. MacMillan

doi:10.1021/jacs.4c04477

Free-Radical Deoxygenative Amination of Alcohols via Copper Metallaphotoredox Catalysis

William P. Carson, Artem V. Tsymbal, Robert W. Pipal, Grant A. Edwards, Joseph R. Martinelli, Albert Cabré, David W.C. MacMillan

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

4 Scopus citations

Abstract

Alcohols are among the most abundant chemical feedstocks, yet they remain vastly underutilized as coupling partners in transition metal catalysis. Herein, we describe a copper metallaphotoredox manifold for the open shell deoxygenative coupling of alcohols with N-nucleophiles to forge C(sp³)-N bonds, a linkage of high value in pharmaceutical agents that is challenging to access via conventional cross-coupling techniques. N-heterocyclic carbene (NHC)-mediated conversion of alcohols into the corresponding alkyl radicals followed by copper-catalyzed C-N coupling renders this platform successful for a broad range of structurally unbiased alcohols and 18 classes of N-nucleophiles.

Original language	English (US)
Pages (from-to)	15681-15687
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	146
Issue number	23
DOIs	https://doi.org/10.1021/jacs.4c04477
State	Published - Jun 12 2024

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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title = "Free-Radical Deoxygenative Amination of Alcohols via Copper Metallaphotoredox Catalysis",

abstract = "Alcohols are among the most abundant chemical feedstocks, yet they remain vastly underutilized as coupling partners in transition metal catalysis. Herein, we describe a copper metallaphotoredox manifold for the open shell deoxygenative coupling of alcohols with N-nucleophiles to forge C(sp3)-N bonds, a linkage of high value in pharmaceutical agents that is challenging to access via conventional cross-coupling techniques. N-heterocyclic carbene (NHC)-mediated conversion of alcohols into the corresponding alkyl radicals followed by copper-catalyzed C-N coupling renders this platform successful for a broad range of structurally unbiased alcohols and 18 classes of N-nucleophiles.",

author = "Carson, {William P.} and Tsymbal, {Artem V.} and Pipal, {Robert W.} and Edwards, {Grant A.} and Martinelli, {Joseph R.} and Albert Cabr{\'e} and MacMillan, {David W.C.}",

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T1 - Free-Radical Deoxygenative Amination of Alcohols via Copper Metallaphotoredox Catalysis

AU - Carson, William P.

AU - Tsymbal, Artem V.

AU - Pipal, Robert W.

AU - Edwards, Grant A.

AU - Martinelli, Joseph R.

AU - Cabré, Albert

AU - MacMillan, David W.C.

PY - 2024/6/12

Y1 - 2024/6/12

N2 - Alcohols are among the most abundant chemical feedstocks, yet they remain vastly underutilized as coupling partners in transition metal catalysis. Herein, we describe a copper metallaphotoredox manifold for the open shell deoxygenative coupling of alcohols with N-nucleophiles to forge C(sp3)-N bonds, a linkage of high value in pharmaceutical agents that is challenging to access via conventional cross-coupling techniques. N-heterocyclic carbene (NHC)-mediated conversion of alcohols into the corresponding alkyl radicals followed by copper-catalyzed C-N coupling renders this platform successful for a broad range of structurally unbiased alcohols and 18 classes of N-nucleophiles.

AB - Alcohols are among the most abundant chemical feedstocks, yet they remain vastly underutilized as coupling partners in transition metal catalysis. Herein, we describe a copper metallaphotoredox manifold for the open shell deoxygenative coupling of alcohols with N-nucleophiles to forge C(sp3)-N bonds, a linkage of high value in pharmaceutical agents that is challenging to access via conventional cross-coupling techniques. N-heterocyclic carbene (NHC)-mediated conversion of alcohols into the corresponding alkyl radicals followed by copper-catalyzed C-N coupling renders this platform successful for a broad range of structurally unbiased alcohols and 18 classes of N-nucleophiles.

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Free-Radical Deoxygenative Amination of Alcohols via Copper Metallaphotoredox Catalysis

Abstract

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