Allyl‐Palladium‐Catalyzed α,β‐Dehydrogenation of Carboxylic Acids via Enediolates

A highly practical and step‐economic α,β‐dehydrogenation of carboxylic acids via enediolates is reported through the use of allyl‐palladium catalysis. Dianions underwent smooth dehydrogenation when generated using Zn(TMP)2⋅2 LiCl as a base in the presence of excess ZnCl2, thus avoiding the typical d...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2017-10, Vol.56 (42), p.13122-13125
Main Authors: Zhao, Yizhou, Chen, Yifeng, Newhouse, Timothy R.
Format: Article
Language:English
Subjects:
carbanions
Carboxylic acids
Catalysis
Decarboxylation
Dehydrogenation
Palladium
Substrates
synthetic methods
Zinc
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Summary:A highly practical and step‐economic α,β‐dehydrogenation of carboxylic acids via enediolates is reported through the use of allyl‐palladium catalysis. Dianions underwent smooth dehydrogenation when generated using Zn(TMP)2⋅2 LiCl as a base in the presence of excess ZnCl2, thus avoiding the typical decarboxylation pathway of these substrates. Direct access to 2‐enoic acids allows derivatization by numerous approaches. All about that dianion: Instead of decarboxylation, allyl‐palladium catalysis allows dehydrogenation of carboxylic acids to form enoic acids via enediolates. The dianions underwent smooth dehydrogenation when generated using Zn(TMP)2⋅2 LiCl as a base in the presence of excess ZnCl2. TMP=2,2,6,6‐tetramethylpiperidine.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201706893