Palladium-Catalyzed Enantioselective Intermolecular Coupling of Phenols and Allylic Alcohols

An enantioselective intermolecular coupling of oxygen nucleophiles and allylic alcohols to give β-aryloxycarbonyl compounds is disclosed using a chiral pyridine oxazoline-ligated palladium catalyst under mild conditions. As opposed to the formation of traditional Wacker-type products, enantioselecti...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2016-12, Vol.138 (49), p.15881-15884
Main Authors: Race, Nicholas J, Schwalm, Cristiane S, Nakamuro, Takayuki, Sigman, Matthew S
Format: Article
Language:English
Subjects:
Catalysis
Molecular Structure
Palladium - chemistry
Phenols - chemical synthesis
Phenols - chemistry
Propanols - chemical synthesis
Propanols - chemistry
Stereoisomerism
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Summary:An enantioselective intermolecular coupling of oxygen nucleophiles and allylic alcohols to give β-aryloxycarbonyl compounds is disclosed using a chiral pyridine oxazoline-ligated palladium catalyst under mild conditions. As opposed to the formation of traditional Wacker-type products, enantioselective migratory insertion is followed by β-hydride elimination toward the adjacent alcohol. Deuterium labeling experiments suggest a syn-migratory insertion of the alkene into the Pd–O bond. A broad scope of phenols, various allylic alcohols, and an alkyl hydroperoxide are viable coupling partners in this process.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.6b11486