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

[Image: see text] 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 fluor...

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Autores principales: Okuda, Yasuhiro, Xu, Jie, Ishida, Takumi, Wang, Chen-an, Nishihara, Yasushi
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2018
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6644556/
https://www.ncbi.nlm.nih.gov/pubmed/31458033
http://dx.doi.org/10.1021/acsomega.8b02155
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author Okuda, Yasuhiro
Xu, Jie
Ishida, Takumi
Wang, Chen-an
Nishihara, Yasushi
author_facet Okuda, Yasuhiro
Xu, Jie
Ishida, Takumi
Wang, Chen-an
Nishihara, Yasushi
author_sort Okuda, Yasuhiro
collection PubMed
description [Image: see text] 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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spelling pubmed-66445562019-08-27 Nickel-Catalyzed Decarbonylative Alkylation of Aroyl Fluorides Assisted by Lewis-Acidic Organoboranes Okuda, Yasuhiro Xu, Jie Ishida, Takumi Wang, Chen-an Nishihara, Yasushi ACS Omega [Image: see text] 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. American Chemical Society 2018-10-12 /pmc/articles/PMC6644556/ /pubmed/31458033 http://dx.doi.org/10.1021/acsomega.8b02155 Text en Copyright © 2018 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
spellingShingle Okuda, Yasuhiro
Xu, Jie
Ishida, Takumi
Wang, Chen-an
Nishihara, Yasushi
Nickel-Catalyzed Decarbonylative Alkylation of Aroyl Fluorides Assisted by Lewis-Acidic Organoboranes
title Nickel-Catalyzed Decarbonylative Alkylation of Aroyl Fluorides Assisted by Lewis-Acidic Organoboranes
title_full Nickel-Catalyzed Decarbonylative Alkylation of Aroyl Fluorides Assisted by Lewis-Acidic Organoboranes
title_fullStr Nickel-Catalyzed Decarbonylative Alkylation of Aroyl Fluorides Assisted by Lewis-Acidic Organoboranes
title_full_unstemmed Nickel-Catalyzed Decarbonylative Alkylation of Aroyl Fluorides Assisted by Lewis-Acidic Organoboranes
title_short Nickel-Catalyzed Decarbonylative Alkylation of Aroyl Fluorides Assisted by Lewis-Acidic Organoboranes
title_sort nickel-catalyzed decarbonylative alkylation of aroyl fluorides assisted by lewis-acidic organoboranes
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6644556/
https://www.ncbi.nlm.nih.gov/pubmed/31458033
http://dx.doi.org/10.1021/acsomega.8b02155
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