TY - JOUR
T1 - Electrochemically Driven, Ni-Catalyzed Aryl Amination
T2 - Scope, Mechanism, and Applications
AU - Kawamata, Yu
AU - Vantourout, Julien C.
AU - Hickey, David P.
AU - Bai, Peng
AU - Chen, Longrui
AU - Hou, Qinglong
AU - Qiao, Wenhua
AU - Barman, Koushik
AU - Edwards, Martin A.
AU - Garrido-Castro, Alberto F.
AU - Degruyter, Justine N.
AU - Nakamura, Hugh
AU - Knouse, Kyle
AU - Qin, Chuanguang
AU - Clay, Khalyd J.
AU - Bao, Denghui
AU - Li, Chao
AU - Starr, Jeremy T.
AU - Garcia-Irizarry, Carmen
AU - Sach, Neal
AU - White, Henry S.
AU - Neurock, Matthew
AU - Minteer, Shelley D.
AU - Baran, Phil S.
N1 - Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/4/17
Y1 - 2019/4/17
N2 - C-N cross-coupling is one of the most valuable and widespread transformations in organic synthesis. Largely dominated by Pd- and Cu-based catalytic systems, it has proven to be a staple transformation for those in both academia and industry. The current study presents the development and mechanistic understanding of an electrochemically driven, Ni-catalyzed method for achieving this reaction of high strategic importance. Through a series of electrochemical, computational, kinetic, and empirical experiments, the key mechanistic features of this reaction have been unraveled, leading to a second generation set of conditions that is applicable to a broad range of aryl halides and amine nucleophiles including complex examples on oligopeptides, medicinally relevant heterocycles, natural products, and sugars. Full disclosure of the current limitations and procedures for both batch and flow scale-ups (100 g) are also described.
AB - C-N cross-coupling is one of the most valuable and widespread transformations in organic synthesis. Largely dominated by Pd- and Cu-based catalytic systems, it has proven to be a staple transformation for those in both academia and industry. The current study presents the development and mechanistic understanding of an electrochemically driven, Ni-catalyzed method for achieving this reaction of high strategic importance. Through a series of electrochemical, computational, kinetic, and empirical experiments, the key mechanistic features of this reaction have been unraveled, leading to a second generation set of conditions that is applicable to a broad range of aryl halides and amine nucleophiles including complex examples on oligopeptides, medicinally relevant heterocycles, natural products, and sugars. Full disclosure of the current limitations and procedures for both batch and flow scale-ups (100 g) are also described.
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U2 - 10.1021/jacs.9b01886
DO - 10.1021/jacs.9b01886
M3 - Article
C2 - 30905151
AN - SCOPUS:85064123598
SN - 0002-7863
VL - 141
SP - 6392
EP - 6402
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 15
ER -