title: A Metallacycle Fragmentation Strategy for Vinyl Transfer from Enol Carboxylates to Secondary Alcohol C-H Bonds via Osmium- or Ruthenium-Catalyzed Transfer Hydrogenation.
abstract: A strategy for catalytic vinyl transfer from enol carboxylates to activated secondary alcohol C-H bonds is described. Using XPhos-modified ruthenium(0) or osmium(0) complexes, enol carboxylate-carbonyl oxidative coupling forms transient β-acyloxy-oxametallacycles, which eliminate carboxylate to deliver allylic ruthenium(II) or osmium(II) alkoxides. Reduction of the metal(II) salt via hydrogen transfer from the secondary alcohol reactant releases the product of carbinol C-H vinylation and regenerates ketone and zero-valent catalyst.
authors.affiliation: Department of Chemistry, University of Texas at Austin, Austin, Texas 78712, United States.
authors.forename: Boyoung Y
authors.initials: BY
authors.lastname: Park
authors.affiliation: Department of Chemistry, University of Texas at Austin, Austin, Texas 78712, United States.
authors.forename: Tom
authors.initials: T
authors.lastname: Luong
authors.affiliation: Department of Chemistry, University of Texas at Austin, Austin, Texas 78712, United States.
authors.forename: Hiroki
authors.initials: H
authors.lastname: Sato
authors.affiliation: Department of Chemistry, University of Texas at Austin, Austin, Texas 78712, United States.
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Krische
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D002264:Carboxylic Acids / Q000737:chemistry*; D002384:Catalysis; D056831:Coordination Complexes / Q000737:chemistry; D006865:Hydrogenation; D009992:Osmium / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D014753:Vinyl Compounds / Q000737:chemistry*
chemical_list: D000438:Alcohols; D002264:Carboxylic Acids; D056831:Coordination Complexes; D014753:Vinyl Compounds; D009992:Osmium; D012428:Ruthenium