title: Profiling the tuneable R-SMS-Phos structure in the rhodium(I)-catalyzed hydrogenation of olefins: the last stand?
abstract: A diversified family of enantiopure P-stereogenic "R-SMS-Phos" {R-SMS-Phos = 1,2-bis[(o-RO-phenyl)(phenyl)phosphino]ethane} ligands wherein R = branched or heteroatom-substituted alkyl, aralkyl, silyl, acyl, sulfonyl, etc. was screened for the Rh(I)-catalyzed hydrogenation of a representative set of olefinic substrates. This systematic and detailed investigation revealed a marked beneficial impact on enantioselectivity and catalyst activity in comparison to Knowles' ultimate DiPAMP {DiPAMP = 1,2-bis[(o-anisyl)(phenyl)phosphino]ethane} design. Mutant ligands with highly enhanced properties possessing particular features wherein the DiPAMP structure is found embedded were identified.
authors.affiliation: National Institute of Chemistry, Hajdrihova 19, SI-1001, Ljubljana, Slovenia. mstephan@phosphoenix.com
authors.forename: Michel
authors.initials: M
authors.lastname: Stephan
authors.forename: Damjan
authors.initials: D
authors.lastname: Šterk
authors.forename: Borut
authors.initials: B
authors.lastname: Zupančič
authors.forename: Barbara
authors.initials: B
authors.lastname: Mohar
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D004980:Ethane / Q000031:analogs & derivatives / Q000737:chemistry*; D006865:Hydrogenation; D008024:Ligands; D008968:Molecular Conformation; D015394:Molecular Structure; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000475:Alkenes; D008024:Ligands; D012238:Rhodium; D004980:Ethane