title: Palladium-Catalyzed Enantioselective Intermolecular Coupling of Phenols and Allylic Alcohols.
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.
authors.affiliation: Department of Chemistry, University of Utah , 315 S 1400 E, Salt Lake City, Utah 84112, United States.
authors.forename: Nicholas J
authors.initials: NJ
authors.lastname: Race
authors.affiliation: Department of Chemistry, University of Utah , 315 S 1400 E, Salt Lake City, Utah 84112, United States.
authors.forename: Cristiane S
authors.initials: CS
authors.lastname: Schwalm
authors.affiliation: Department of Chemistry, University of Utah , 315 S 1400 E, Salt Lake City, Utah 84112, United States.
authors.forename: Takayuki
authors.initials: T
authors.lastname: Nakamuro
authors.affiliation: Department of Chemistry, University of Utah , 315 S 1400 E, Salt Lake City, Utah 84112, United States.
authors.forename: Matthew S
authors.initials: MS
authors.lastname: Sigman
mesh_terms: D002384:Catalysis; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*; D010636:Phenols / Q000138:chemical synthesis* / Q000737:chemistry; D020005:Propanols / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D010636:Phenols; D020005:Propanols; C006463:allyl alcohol; D010165:Palladium