title: Chiral ditopic cyclophosphazane (CycloP) ligands: synthesis, coordination chemistry, and application in asymmetric catalysis.
abstract: A series of dichlorocyclophosphazanes [{ClP(μ-NR)}2 ] containing chiral and achiral R groups was obtained from simple commercially available amines and PCl3 . Their condensation reactions with axially chiral biaryl diols yielded ansa-bridged chiral cyclophosphazane (CycloP) ligands. This highly modular methodology allows extensive elaboration of the ligand set, in which the chirality can be introduced at the diol bridge and/or the amido R group. This provides the possibility to observe match and mismatch effects in catalysis. A series of twenty CycloP ligands was synthesized and characterized by multinuclear NMR spectroscopy, HRMS, elemental analysis, and in selected cases, single-crystal X-ray diffraction. These studies show that all of the ditopic CycloP ligands are C2 symmetric, rendering their metal coordination sites symmetry equivalent. Two well-established enantioselective reactions were explored by using late-transition metal CycloP complexes as catalysts; the gold-catalyzed hydroamination of γ-allenyl sulfonamides and the asymmetric nickel-catalyzed three-component coupling of a diene and an aldehyde. The steric demands of the CycloP ligands have a subtle influence on the reactivity and selectivity observed in both reactions. Good enantiomeric ratios (e.r.) as high as 89:11 in the gold-catalyzed reaction and 92:8 in the nickel-catalyzed bis-homoallylation reaction were observed.
authors.affiliation: Anorganisch Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg (Germany), Fax: (+49) 6221-54-5609.
authors.forename: Torsten
authors.initials: T
authors.lastname: Roth
authors.forename: Hubert
authors.initials: H
authors.lastname: Wadepohl
authors.forename: Dominic S
authors.initials: DS
authors.lastname: Wright
authors.forename: Lutz H
authors.initials: LH
authors.lastname: Gade
keywords: X-ray diffraction; asymmetric catalysis; chiral ligands; phosphazanes; synthetic methods