title: Chiral-anion-dependent inversion of diastereo- and enantioselectivity in carbonyl crotylation via ruthenium-catalyzed butadiene hydrohydroxyalkylation.
abstract: The ruthenium catalyst generated in situ from H(2)Ru(CO)(PPh(3))(3), (S)-SEGPHOS, and a TADDOL-derived phosphoric acid promotes butadiene hydrohydroxyalkylation to form enantiomerically enriched products. Notably, the observed diastereo- and enantioselectivity is the opposite of that observed using BINOL-derived phosphate counterions in combination with (S)-SEGPHOS, the same enantiomer of the chiral ligand. Match/mismatch effects between the chiral ligand and the chiral TADDOL-phosphate counterion are described. For the first time, single-crystal X-ray diffraction data for a ruthenium complex modified by a chiral phosphate counterion are reported.
authors.affiliation: Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, Texas 78712, USA.
authors.forename: Emma L
authors.initials: EL
authors.lastname: McInturff
authors.forename: Eiji
authors.initials: E
authors.lastname: Yamaguchi
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Krische
mesh_terms: D000478:Alkylation; D002070:Butadienes / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D004149:Dioxoles / Q000737:chemistry; D008958:Models, Molecular; D010710:Phosphates / Q000737:chemistry; D010756:Phosphoric Acids / Q000737:chemistry; D012428:Ruthenium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D002070:Butadienes; D004149:Dioxoles; D010710:Phosphates; D010756:Phosphoric Acids; D012428:Ruthenium; C030242:phosphoric acid; C040539:1,3-benzodioxole