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Efficient Pd‐Catalyzed Regio‐ and Stereoselective Carboxylation of Allylic Alcohols with Formic Acid
Author(s) -
Fu MingChen,
Shang Rui,
Cheng WanMin,
Fu Yao
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201701971
Subject(s) - chemistry , carbonylation , allylic rearrangement , stereoselectivity , carboxylation , catalysis , electrophile , xantphos , isomerization , palladium , succinic anhydride , organic chemistry , ligand (biochemistry) , carbon monoxide , medicinal chemistry , formic acid , carboxylic acid , biochemistry , receptor
Formic acid is efficiently used as a C1 source to directly carboxylate allylic alcohols in the presence of a low loading of palladium catalyst and acetic anhydride as additive to afford β,γ‐unsaturated carboxylic acids with excellent chemo‐, regio‐, and stereoselectivity. The reaction proceeds through a carbonylation process with in situ‐generated carbon monoxide under mild conditions, avoiding the use of high‐pressure gaseous CO. A bisphosphine ligand with a large bite angle (4,5‐bis{diphenylphosphino}‐9,9‐dimethylxanthene, Xantphos) was found to be uniquely effective for this transformation. The regio‐ and stereoconvergence of this reaction is ascribed to the thermodynamically favored isomerization of the allylic electrophile in the presence of the palladium catalyst.