title: Alkynes as allylmetal equivalents in redox-triggered C-C couplings to primary alcohols: (Z)-homoallylic alcohols via ruthenium-catalyzed propargyl C-H oxidative addition.
abstract: The cationic ruthenium catalyst generated upon the acid-base reaction of H2Ru(CO)(PPh3)3 and 2,4,6-(2-Pr)3PhSO3H promotes the redox-triggered C-C coupling of 2-alkynes and primary alcohols to form (Z)-homoallylic alcohols with good to complete control of olefin geometry. Deuterium labeling studies, which reveal roughly equal isotopic compositions at the allylic and distal vinylic positions, along with other data, corroborate a catalytic mechanism involving ruthenium(0)-mediated allene-aldehyde oxidative coupling to form a transient oxaruthenacycle, an event that ultimately defines (Z)-olefin stereochemistry.
authors: Department of Chemistry, University of Texas at Austin , Austin, Texas 78712, United States.
authors: Boyoung Y
authors: BY
authors: Park
authors: Khoa D
authors: KD
authors: Nguyen
authors: Mani Raj
authors: MR
authors: Chaulagain
authors: Venukrishnan
authors: V
authors: Komanduri
authors: Michael J
authors: MJ
authors: Krische
mesh_terms: D000438:Alcohols / Q000737:chemistry; D000480:Alkynes / Q000737:chemistry*; D000498:Allyl Compounds / Q000737:chemistry*; D002384:Catalysis; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D020005:Propanols / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000438:Alcohols; D000480:Alkynes; D000498:Allyl Compounds; D009942:Organometallic Compounds; D020005:Propanols; D012428:Ruthenium; C028255:propargyl alcohol