title: Redox-triggered C-C coupling of alcohols and vinyl epoxides: diastereo- and enantioselective formation of all-carbon quaternary centers via tert-(hydroxy)-prenylation.
abstract: Iridium catalyzed primary alcohol oxidation triggers reductive C-O bond cleavage of isoprene oxide to form aldehyde-allyliridium pairs that combine to form products of tert-(hydroxy)-prenylation, a motif found in >2000 terpenoid natural products. Curtin-Hammett effects are exploited to enforce high levels of anti-diastereo- and enantioselectivity in the formation of an all-carbon quaternary center. The present redox-triggered carbonyl additions occur in the absence of stoichiometric byproducts, premetalated reagents, and discrete alcohol-to-aldehyde redox manipulations.
authors.affiliation: Department of Chemistry, University of Texas at Austin , Austin, Texas 78712, United States.
authors.forename: Jiajie
authors.initials: J
authors.lastname: Feng
authors.forename: Victoria J
authors.initials: VJ
authors.lastname: Garza
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Krische
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D002384:Catalysis; D004852:Epoxy Compounds / Q000737:chemistry*; D007495:Iridium / Q000737:chemistry; D015394:Molecular Structure; D010084:Oxidation-Reduction; D054876:Prenylation; D013237:Stereoisomerism; D013729:Terpenes / Q000138:chemical synthesis* / Q000737:chemistry; D014753:Vinyl Compounds / Q000737:chemistry*
chemical_list: D000438:Alcohols; D004852:Epoxy Compounds; D013729:Terpenes; D014753:Vinyl Compounds; D007495:Iridium