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. 2016 Dec 14;138(49):15881-15884.
doi: 10.1021/jacs.6b11486. Epub 2016 Dec 1.

Palladium-Catalyzed Enantioselective Intermolecular Coupling of Phenols and Allylic Alcohols

Nicholas J Race  1 , Cristiane S Schwalm  1 , Takayuki Nakamuro  1 , Matthew S Sigman  1
Affiliations

Palladium-Catalyzed Enantioselective Intermolecular Coupling of Phenols and Allylic Alcohols

Nicholas J Race et al. J Am Chem Soc. .

Abstract

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.

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Figures

Scheme 1
Scheme 1
Wacker-type Alkene Functionalization
Scheme 2
Scheme 2
Mechanistic Analysis
See this image and copyright information in PMC

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