Copper-Catalyzed Electrophilic Amidation of Organotrifluoroborates with Use of N-Methoxyamides

Shona Banjo; Eiko Nakasuji; Tatsuhiko Meguro; Takaaki Sato; Noritaka Chida

doi:10.1002/chem.201901145

Copper-Catalyzed Electrophilic Amidation of Organotrifluoroborates with Use of N-Methoxyamides

Shona Banjo, Eiko Nakasuji, Tatsuhiko Meguro, Takaaki Sato, Noritaka Chida

Department of Applied Chemistry

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

11 Citations (Scopus)

Abstract

A copper-catalyzed electrophilic amidation of aryltrifluoroborates with use of N-methoxyamides is reported. The reaction shows high functional group compatibility derived from two distinct features: 1) the high stability of the N-methoxyamides and 2) the nonbasic mild conditions in the presence of LiCl. The developed method can also be applied to the synthesis of enamides, which are widely distributed in natural products. Preliminary mechanistic studies suggest that the initial step is the transmetalation of the aryltrifluoroborate by the assistance of LiCl, and the resulting aryl copper intermediate provides the anilide through non-S_N2 oxidative addition to the N-methoxyamide and subsequent reductive elimination.

Original language	English
Pages (from-to)	7941-7947
Number of pages	7
Journal	Chemistry - A European Journal
Volume	25
Issue number	33
DOIs	https://doi.org/10.1002/chem.201901145
Publication status	Published - 2019 Jun 12

Keywords

amides
copper catalyst
electrophilic reaction
enamides
organotrifluoroborates
synthetic methods

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Organic Chemistry

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10.1002/chem.201901145

Cite this

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title = "Copper-Catalyzed Electrophilic Amidation of Organotrifluoroborates with Use of N-Methoxyamides",

abstract = "A copper-catalyzed electrophilic amidation of aryltrifluoroborates with use of N-methoxyamides is reported. The reaction shows high functional group compatibility derived from two distinct features: 1) the high stability of the N-methoxyamides and 2) the nonbasic mild conditions in the presence of LiCl. The developed method can also be applied to the synthesis of enamides, which are widely distributed in natural products. Preliminary mechanistic studies suggest that the initial step is the transmetalation of the aryltrifluoroborate by the assistance of LiCl, and the resulting aryl copper intermediate provides the anilide through non-SN2 oxidative addition to the N-methoxyamide and subsequent reductive elimination.",

keywords = "amides, copper catalyst, electrophilic reaction, enamides, organotrifluoroborates, synthetic methods",

author = "Shona Banjo and Eiko Nakasuji and Tatsuhiko Meguro and Takaaki Sato and Noritaka Chida",

note = "Funding Information: This research was supported by a Grant-in-Aid for Scientific Research (C) from MEXT (15K05436), and the Tobe Maki scholarship foundation to E.N. Synthetic assistance from Ms. Kanami Fujita is gratefully acknowledged. Publisher Copyright: {\textcopyright} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

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doi = "10.1002/chem.201901145",

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AU - Banjo, Shona

AU - Nakasuji, Eiko

AU - Meguro, Tatsuhiko

AU - Sato, Takaaki

AU - Chida, Noritaka

N1 - Funding Information: This research was supported by a Grant-in-Aid for Scientific Research (C) from MEXT (15K05436), and the Tobe Maki scholarship foundation to E.N. Synthetic assistance from Ms. Kanami Fujita is gratefully acknowledged. Publisher Copyright: © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2019/6/12

Y1 - 2019/6/12

N2 - A copper-catalyzed electrophilic amidation of aryltrifluoroborates with use of N-methoxyamides is reported. The reaction shows high functional group compatibility derived from two distinct features: 1) the high stability of the N-methoxyamides and 2) the nonbasic mild conditions in the presence of LiCl. The developed method can also be applied to the synthesis of enamides, which are widely distributed in natural products. Preliminary mechanistic studies suggest that the initial step is the transmetalation of the aryltrifluoroborate by the assistance of LiCl, and the resulting aryl copper intermediate provides the anilide through non-SN2 oxidative addition to the N-methoxyamide and subsequent reductive elimination.

AB - A copper-catalyzed electrophilic amidation of aryltrifluoroborates with use of N-methoxyamides is reported. The reaction shows high functional group compatibility derived from two distinct features: 1) the high stability of the N-methoxyamides and 2) the nonbasic mild conditions in the presence of LiCl. The developed method can also be applied to the synthesis of enamides, which are widely distributed in natural products. Preliminary mechanistic studies suggest that the initial step is the transmetalation of the aryltrifluoroborate by the assistance of LiCl, and the resulting aryl copper intermediate provides the anilide through non-SN2 oxidative addition to the N-methoxyamide and subsequent reductive elimination.

KW - amides

KW - copper catalyst

KW - electrophilic reaction

KW - enamides

KW - organotrifluoroborates

KW - synthetic methods

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JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

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ER -

Copper-Catalyzed Electrophilic Amidation of Organotrifluoroborates with Use of N-Methoxyamides

Abstract

Keywords

ASJC Scopus subject areas

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