Nickel-Catalyzed Decarbonylative Alkylation of Aroyl Fluorides Assisted by Lewis-Acidic Organoboranes

• Published in: ACS omega Vol. 3; no. 10; pp. 13129 - 13140
• Main Authors: Okuda, Yasuhiro, Xu, Jie, Ishida, Takumi, Wang, Chen-an, Nishihara, Yasushi
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 31.10.2018
• ISSN: 2470-1343; 2470-1343
• DOI: 10.1021/acsomega.8b02155

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.