New chiral α-aminophosphine oxides and sulfides:: an unprecedented rhodium-catalyzed ligand epimerization

被引:20
作者
Andrieu, J [1 ]
Camus, JM [1 ]
Poli, R [1 ]
Richard, P [1 ]
机构
[1] Univ Bourgogne 1, Fac Sci Gabriel, Lab Synth & Electrosynth Organomet, F-21000 Dijon, France
关键词
D O I
10.1039/b100217l
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
New chiral alpha -aminophosphine oxide N,P(O) and sulfide N,P(S) ligands have been prepared in one-pot syntheses by addition of Ph2PH to (S)-PhCH=NCH(Ph)CH3, followed by oxidation with O-2 or S-8. Crystallization from cold methanol leads to the isolation of an enantiomerically pure single N,P(O) diastereomer and to a 1:1 mixture of the two N,P(S) diastereomers. The coordination chemistry of these ligands with [RhCl(COD)](2) and [RhCl(CO)(2)](2) has been investigated under argon and syngas. At high temperatures, a P-C oxidative addition of the N,P(O) ligand followed by imine elimination leads to several hydrido rhodium species. The complexes containing an N,P(S) ligand undergo the same process at room temperature. Catalytic amounts of the rhodium complexes catalyze the epimerization of the N,P(S) ligand under argon at room temperature, the dicarbonyl complex being 14 times more active than the COD complex. The same catalyzed epimerization takes also place for the N,P(O) ligand, but much more slowly, and only at 35 degreesC and under a syngas pressure. Possible mechanisms for this catalytic process are discussed. Catalytic tests in styrene hydroformylation have shown high activities and regioselectivities, but no enantioselectivity, for the N,P(O)-containing rhodium complexes.
引用
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页码:1015 / 1023
页数:9
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