TY - JOUR
T1 - Nickel-Catalyzed Decarbonylative Alkylation of Aroyl Fluorides Assisted by Lewis-Acidic Organoboranes
AU - Okuda, Yasuhiro
AU - Xu, Jie
AU - Ishida, Takumi
AU - Wang, Chen An
AU - Nishihara, Yasushi
N1 - Funding Information:
This work was supported by ACT-C, JST Grant Number JPMJCR12YW, Japan, and a Grant-in-Aid from JSPS (15J00293 to Y.O.). The authors gratefully thank Dr. Xi-Chao Chen for preparation of aroyl fluorides and Megumi Kosaka and Motonari Kobayashi at the Department of Instrumental Analysis, Advanced Science Research Center, Okayama University, for the measurements of elemental analyses and the SC-NMR Laboratory of Okayama University for the NMR spectral measurements.
Publisher Copyright:
Copyright © 2018 American Chemical Society.
PY - 2018/10/12
Y1 - 2018/10/12
N2 - Herein, nickel-catalyzed decarbonylative C-F bond alkylation of aroyl fluorides with organoboron reagents is reported. Aroyl fluorides are more chemically stable than the corresponding aroyl chlorides and can be readily synthesized from the corresponding carboxylic acids. The fluoronickel intermediate formed via oxidative addition interacts with Lewis-acidic trialkylboranes, and the subsequent decarbonylative alkylation proceeds. This new synthetic methodology allows 1,2-bifunctionalization of aromatic carboxylic acids via palladium-catalyzed ortho-C-H arylation. In addition, an unprecedented 1,4-nickel migration on ortho-arylated aroyl fluorides was observed. As a demonstration of the synthetic utility of the present reaction, the sequential 1-alkyl-2-arylation of 3-hydroxy-2-naphthoic acid was accomplished via chemoselective alkylation at a fluorocarbonyl moiety and the subsequent C-O bond arylation at an acetoxy group.
AB - Herein, nickel-catalyzed decarbonylative C-F bond alkylation of aroyl fluorides with organoboron reagents is reported. Aroyl fluorides are more chemically stable than the corresponding aroyl chlorides and can be readily synthesized from the corresponding carboxylic acids. The fluoronickel intermediate formed via oxidative addition interacts with Lewis-acidic trialkylboranes, and the subsequent decarbonylative alkylation proceeds. This new synthetic methodology allows 1,2-bifunctionalization of aromatic carboxylic acids via palladium-catalyzed ortho-C-H arylation. In addition, an unprecedented 1,4-nickel migration on ortho-arylated aroyl fluorides was observed. As a demonstration of the synthetic utility of the present reaction, the sequential 1-alkyl-2-arylation of 3-hydroxy-2-naphthoic acid was accomplished via chemoselective alkylation at a fluorocarbonyl moiety and the subsequent C-O bond arylation at an acetoxy group.
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U2 - 10.1021/acsomega.8b02155
DO - 10.1021/acsomega.8b02155
M3 - Article
AN - SCOPUS:85054997929
VL - 3
SP - 13129
EP - 13140
JO - ACS Omega
JF - ACS Omega
SN - 2470-1343
IS - 10
ER -