Transition-metal-free decarboxylative bromination of aromatic carboxylic acids

Chemical Science
Jacob M QuibellIgor Larrosa

Abstract

Methods for the conversion of aliphatic acids to alkyl halides have progressed significantly over the past century, however, the analogous decarboxylative bromination of aromatic acids has remained a longstanding challenge. The development of efficient methods for the synthesis of aryl bromides is of great importance as they are versatile reagents in synthesis and are present in many functional molecules. Herein we report a transition metal-free decarboxylative bromination of aromatic acids. The reaction is applicable to many electron-rich aromatic and heteroaromatic acids which have previously proved poor substrates for Hunsdiecker-type reactions. In addition, our preliminary mechanistic study suggests that radical intermediates are not involved in this reaction, which is in contrast to classical Hunsdiecker-type reactivity. Overall, the process demonstrates a useful method for producing valuable reagents from inexpensive and abundant starting materials.

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Citations

Nov 6, 2018·Angewandte Chemie·Shubhadip MallickArmido Studer
Dec 24, 2018·Angewandte Chemie·Xiang-Wei LiuRuben Martin
May 18, 2019·Chemical Communications : Chem Comm·Jacob M QuibellIgor Larrosa
Apr 17, 2019·Angewandte Chemie·Simon RohrbachJohn A Murphy
Jan 2, 2020·Environmental Science and Pollution Research International·Ram DhakalHans-Joachim Lehmler
Jun 3, 2021·Organic & Biomolecular Chemistry·Ruchi Sharma, M Ramu Yadav
Jun 8, 2021·Chemical Science·Tsubasa MatsuzawaSuguru Yoshida
Jan 4, 2020·The Journal of Organic Chemistry·Dinesh G PatelFrank A Novak
Nov 18, 2020·Chemical Reviews·Andrii VarenikovMark Gandelman

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Methods Mentioned

BETA
column chromatography
NMR

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