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Bismuth-Mediated α-Arylation of Acidic Diketones with ortho-Substituted Boronic Acids

Ruffell, Katie; Argent, Stephen P.; Ling, Kenneth B.; Ball, Liam T.

Bismuth-Mediated α-Arylation of Acidic Diketones with ortho-Substituted Boronic Acids Thumbnail


Authors

Katie Ruffell

Kenneth B. Ling

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LIAM BALL Liam.Ball@nottingham.ac.uk
Associate Professor



Abstract

The α-arylation of cyclic and fluoroalkyl 1,3-diketones is made challenging by the highly stabilized nature of the corresponding enolates, and is especially difficult for sterically demanding aryl partners. As a general solution to this problem, we report the Bi-mediated oxidative coupling of acidic diones and ortho-substituted arylboronic acids. Starting from a bench-stable bismacycle precursor, a sequence of B-to-Bi transmetallation, oxidation and C−C bond formation furnishes the arylated diones. Development of methodology that tolerates both sensitive functionality and steric demand is supported by interrogation of key reactive intermediates. Application of our strategy to cyclic diones enables the concise synthesis of important agrochemical intermediates which were previously prepared using toxic Pb reagents. This methodology also enables the first ever arylation of fluoroalkyl diones which, upon condensation with hydrazine, provides direct access to valuable fluoroalkyl pyrazoles.

Journal Article Type Article
Acceptance Date Aug 10, 2022
Online Publication Date Aug 11, 2022
Publication Date Oct 4, 2022
Deposit Date Aug 18, 2022
Publicly Available Date Aug 12, 2023
Journal Angewandte Chemie - International Edition
Print ISSN 1433-7851
Electronic ISSN 1521-3773
Publisher Wiley
Peer Reviewed Peer Reviewed
Volume 61
Issue 40
Article Number e202210840
DOI https://doi.org/10.1002/anie.202210840
Keywords General Chemistry; Catalysis
Public URL https://nottingham-repository.worktribe.com/output/10080650
Publisher URL https://onlinelibrary.wiley.com/doi/10.1002/anie.202210840

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