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Chemoselective Decarboxylative Protonation Enabled by Cooperative Earth-Abundant Element Catalysis.

ABSTRACT: Decarboxylative protonation is a general deletion tactic to replace polar carboxylic acid groups with hydrogen or its isotope. Current methods rely on the pre-activation of acids, non-sustainable hydrogen sources, and/or expensive/highly oxidizing photocatalysts, presenting challenges to their wide adoption. Here we show that a cooperative iron/thiol catalyst system can readily achieve this transformation, hydrodecarboxylating a wide range of activated and unactivated carboxylic acids and overcoming scope limitations in previous direct methods. The reaction is readily scaled in batch configuration and can be directly performed in deuterated solvent to afford high yields of d-incorporated products with excellent isotope incorporation efficiency; characteristics not attainable in previous photocatalyzed approaches. Preliminary mechanistic studies indicate a radical mechanism and kinetic results of unactivated acids (KIE=1) are consistent with a light-limited reaction.

SUBMITTER: Lu YC

PROVIDER: S-EPMC9839625 | biostudies-literature | 2023 Jan

REPOSITORIES: biostudies-literature

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Chemoselective Decarboxylative Protonation Enabled by Cooperative Earth-Abundant Element Catalysis.

Lu Yen-Chu YC West Julian G JG

Angewandte Chemie (International ed. in English) 20221208 3

Decarboxylative protonation is a general deletion tactic to replace polar carboxylic acid groups with hydrogen or its isotope. Current methods rely on the pre-activation of acids, non-sustainable hydrogen sources, and/or expensive/highly oxidizing photocatalysts, presenting challenges to their wide adoption. Here we show that a cooperative iron/thiol catalyst system can readily achieve this transformation, hydrodecarboxylating a wide range of activated and unactivated carboxylic acids and overco ...[more]

PMID: 36350328

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