title: Chiral bidentate aminophosphine ligands: synthesis, coordination chemistry and asymmetric catalysis.
abstract: Chiral aminophosphines Ph2PN(R)(CH2)nN(R)PPh2 1-4 [n= 2, R = CH(CH3)(Ph) 1; n= 3, R = CH(CH2CH3)(Ph) 2, n= 2, R = CH(CH3)(1-naphthyl) 3; n= 2, R = CH(CH3)(C6H11) 4] were synthesized by the reaction of ClPPh2 with the appropriate easily accessible enantiopure amine building blocks. For compounds 1 and 2, the corresponding selenides 5 and 6 were prepared to determine the electronic character of the phosphine moieties. By reaction of 1 with either PdCl2(cod) or PdCl(CH3)(cod) the cis-complexes 7 and 8 were obtained. The molecular structure for complex 7, cis-[PdCl2(1)], was determined by X-ray crystallography. Reaction of PtCl2(cod) with 1 or 2 yielded the corresponding monomeric cis-isomers 9 and 10. The rhodium derivative [RhCl(CO)(1)] (11) was obtained as a mixture of cis and trans-isomers. Preliminary results in the rhodium catalyzed hydroformylation of styrene and vinyl acetate, with ee's up to 51% and high regioselectivities, showed the potential of these chiral aminophosphines for homogeneous catalysis.
authors.affiliation: Schuit Institute of Catalysis, Laboratory of Homogeneous Catalysis, Eindhoven University of Technology, P.O. Box 513, 5600 MB, Eindhoven, The Netherlands.
authors.forename: Eric J
authors.initials: EJ
authors.lastname: Zijp
authors.forename: Jarl Ivar
authors.initials: JI
authors.lastname: van der Vlugt
authors.forename: Duncan M
authors.initials: DM
authors.lastname: Tooke
authors.forename: Anthony L
authors.initials: AL
authors.lastname: Spek
authors.forename: Dieter
authors.initials: D
authors.lastname: Vogt