Deerenberg S, Pàmies O, Diéguez M, Claver C, Kamer P C, van Leeuwen P W
Institute of Molecular Chemistry, Universiteit van Amsterdam, Nieuwe Achtergracht 166, 1018 WV Amsterdam, The Netherlands.
J Org Chem. 2001 Nov 16;66(23):7626-31. doi: 10.1021/jo015705d.
We have investigated a series of enantiopure phosphine-phosphite ligands (P(1)-P(2) = ligands 1-4) in the rhodium-catalyzed asymmetric hydrogenation reaction. Intermediate [Rh(P(1)-P(2))(cod)]BF(4) and [Rh(P(1)-P(2))(5)]BF(4) complexes (cod = 1,5-cyclooctadiene; 5 = methyl acetamidoacrylate ester) were observed by (31)P[(1)H] NMR. The [Rh(P(1)-P(2))(cod)]BF(4) complexes were precursors to active catalysts of the asymmetric hydrogenation reaction of several prochiral dehydroamino acid derivatives under mild reaction conditions (1 bar of hydrogen and 20 degrees C). The enantiomeric excess reached up to 99%.
我们研究了一系列对映体纯的膦 - 亚磷酸酯配体(P(1) - P(2) = 配体1 - 4)在铑催化的不对称氢化反应中的情况。通过³¹P[¹H] NMR观察到中间体[Rh(P(1) - P(2))(cod)]BF₄和[Rh(P(1) - P(2))(5)]BF₄配合物(cod = 1,5 - 环辛二烯;5 = 甲基乙酰氨基丙烯酸酯)。[Rh(P(1) - P(2))(cod)]BF₄配合物是几种前手性脱氢氨基酸衍生物在温和反应条件(1巴氢气和20℃)下不对称氢化反应活性催化剂的前体。对映体过量高达99%。