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

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

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.

Citation

Ruffell, K., Argent, S. P., Ling, K. B., & Ball, L. T. (2022). Bismuth-Mediated α-Arylation of Acidic Diketones with ortho-Substituted Boronic Acids. Angewandte Chemie International Edition, 61(40), Article e202210840. https://doi.org/10.1002/anie.202210840

• 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