Palladium‐Catalyzed Decarbonylative Borylation of Carboxylic Acids: Tuning Reaction Selectivity by Computation

Decarbonylative borylation of carboxylic acids is reported. Carbon electrophiles are generated directly after reagent‐enabled decarbonylation of the in situ accessible sterically‐hindered acyl derivative of a carboxylic acid under catalyst controlled conditions. The scope and the potential impact of...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2018-12, Vol.57 (51), p.16721-16726
Main Authors: Liu, Chengwei, Ji, Chong‐Lei, Hong, Xin, Szostak, Michal
Format: Article
Language:English
Subjects:
Acids
Aromatic compounds
Carboxylic acids
Computation
computational chemistry
Controlled conditions
decarbonylation
Decarboxylation
Natural products
Palladium
Reagents
regioselectivity
Selectivity
transition-metal catalysis
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Summary:Decarbonylative borylation of carboxylic acids is reported. Carbon electrophiles are generated directly after reagent‐enabled decarbonylation of the in situ accessible sterically‐hindered acyl derivative of a carboxylic acid under catalyst controlled conditions. The scope and the potential impact of this method are demonstrated in the selective borylation of a variety of aromatics (>50 examples). This strategy was used in the late‐stage derivatization of pharmaceuticals and natural products. Computations reveal the mechanistic details of the unprecedented C−O bond activation of carboxylic acids. By circumventing the challenging decarboxylation, this strategy provides a general synthetic platform to access arylpalladium species for a wide array of bond formations from abundant carboxylic acids. The study shows a powerful combination of experiment and computation to predict decarbonylation selectivity. Predicting selectivity: Decarbonylative borylation of carboxylic acids is reported. By circumventing the challenging decarboxylation, this strategy provides a general synthetic platform to access arylpalladium species for a wide array of bond formations from abundant carboxylic acids. Computations illustrate the origin of activation selectivity.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201810145