title: Direct, redox-neutral prenylation and geranylation of secondary carbinol C-H bonds: C4-regioselectivity in ruthenium-catalyzed C-C couplings of dienes to α-hydroxy esters.
abstract: The ruthenium catalyst generated in situ from Ru(3)(CO)(12) and tricyclohexylphosphine, PCy(3), promotes the redox-neutral C-C coupling of aryl-substituted α-hydroxy esters to isoprene and myrcene at the diene C4-position, resulting in direct carbinol C-H prenylation and geranylation, respectively. This process enables direct conversion of secondary to tertiary alcohols in the absence of stoichiometric byproducts or premetalated reagents, and is the first example of C4-regioselectivity in catalytic C-C couplings of 2-substituted dienes to carbonyl partners. Mechanistic studies corroborate a catalytic cycle involving diene-carbonyl oxidative coupling.
authors.affiliation: Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, Texas 78712, United States.
authors.forename: Joyce C
authors.initials: JC
authors.lastname: Leung
authors.forename: Laina M
authors.initials: LM
authors.lastname: Geary
authors.forename: Te-Yu
authors.initials: TY
authors.lastname: Chen
authors.forename: Jason R
authors.initials: JR
authors.lastname: Zbieg
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Krische
mesh_terms: D002384:Catalysis; D004952:Esters; D009682:Magnetic Resonance Spectroscopy; D000432:Methanol / Q000737:chemistry*; D010084:Oxidation-Reduction; D054876:Prenylation; D012428:Ruthenium / Q000737:chemistry*
chemical_list: D004952:Esters; D012428:Ruthenium; D000432:Methanol