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Zijp EJ, van der Vlugt JI, Tooke DM, Spek AL, Vogt D: Chiral bidentate aminophosphine ligands: synthesis, coordination chemistry and asymmetric catalysis. Dalton Trans. 2005 Feb 7;(3):512-7. Epub 2005 Jan 4.
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. |
6(0,0,1,1) |