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

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2022 Aug 11

PMID 35950691

Authors

Katie Ruffell

Stephen P Argent

Kenneth B Ling

Liam T Ball

Affiliations

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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.

Citing Articles

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PMID: 36251336 PMC: 10099949. DOI: 10.1002/anie.202212873.

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

Ruffell K, Argent S, Ling K, Ball L Angew Chem Int Ed Engl. 2022; 61(40):e202210840.

PMID: 35950691 DOI: 10.1002/anie.202210840.

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