title: C2-symmetric chiral disulfoxide ligands in rhodium-catalyzed 1,4-addition: from ligand synthesis to the enantioselection pathway.
abstract: A family of chiral C(2)-symmetric disulfoxide ligands possessing biaryl atropisomeric backbones has been synthesized by using the Andersen methodology. Complete characterization includes X-ray crystallographic studies of all ligands and some of their rhodium complexes. Their synthesis, optical purity, electronic properties, and catalytic behavior in the prototypical rhodium-catalyzed 1,4-addition of phenylboronic acid to 2-cyclohexen-1-one are presented through an in depth study of this ligand class. Density functional theory calculations on the step of the catalytic cycle that determines the enantioselectivity are presented and reinforce the first hypothetical explanations for the high levels of asymmetric induction observed.
authors.affiliation: Organisch-chemisches Institut, Universität Zürich, Winterthurerstrasse 190, 8057 Zürich, Switzerland.
authors.forename: Ronaldo
authors.initials: R
authors.lastname: Mariz
authors.forename: Albert
authors.initials: A
authors.lastname: Poater
authors.forename: Michele
authors.initials: M
authors.lastname: Gatti
authors.forename: Emma
authors.initials: E
authors.lastname: Drinkel
authors.forename: Justus J
authors.initials: JJ
authors.lastname: Bürgi
authors.forename: Xinjun
authors.initials: X
authors.lastname: Luan
authors.forename: Sascha
authors.initials: S
authors.lastname: Blumentritt
authors.forename: Anthony
authors.initials: A
authors.lastname: Linden
authors.forename: Luigi
authors.initials: L
authors.lastname: Cavallo
authors.forename: Reto
authors.initials: R
authors.lastname: Dorta
mesh_terms: D001897:Boronic Acids / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D003512:Cyclohexanones / Q000138:chemical synthesis* / Q000737:chemistry; D008024:Ligands; D008968:Molecular Conformation; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry; D012238:Rhodium / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D013237:Stereoisomerism; D013454:Sulfoxides / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D001897:Boronic Acids; D003512:Cyclohexanones; D008024:Ligands; D009942:Organometallic Compounds; D013454:Sulfoxides; C028215:2-cyclohexen-1-one; D002244:Carbon; D012238:Rhodium; C010686:benzeneboronic acid