研究了奎宁作手性修饰剂修饰的负载型纳米铑簇合物催化剂(Rh PV P2C2A l2O 3)催化丙酮酸乙酯不对称氢化反应， 在该反应中手性修饰剂奎宁不仅具有手性诱导作用，而且还有明显加速反应的作用；载体C2A l2O 3在促进提高催化剂活性和对映选择性方面也有很重要的影响。在优化的反应条件[20 ℃，7.0M PaH2, c (奎宁) = 3.86×10-3mo lL，四氢呋喃作溶剂]下, 丙酮酸乙酯不对称加氢的转化频率(TO F) 为871h-1, 对映选择性达到了54.7%；反应温度降低到3 ℃时, 对映选择性达到59.2%。

The promotional effect of cationic gemini surfactants for the hydroformylation of 1-dodecene in the organic/aqueous biphasic catalytic system is reported. Cationic gemini surfactants with a flexible spacer (G(Eth), G(But) and G(Hex)) and rigid spacer (G(Xyl)) group were used in the reaction. The critical micelle concentration (CMC) and solubilization of laurylbenzene in gemini surfactant solutions were determined. The influence of the concentration of gemini surfactants and the stirring rate on 1-dodecene hydroformylation were investigated. The reaction results showed that in the biphasic catalytic system the hydroformylation of 1-dodecene catalyzed by RhCl(CO)(TPPTS)2-TPPTS [TPPTS = tris(sodium-m-sulfonatophenyl) phosphine] in the presence of gemini surfactants occurred with higher turn over frequency (TOF) and higher regioselectivity toward linear aldehyde (L/B) than those obtained with the conventional monomeric surfactant CTAB. The phenomena could be attributed to the fact that the gemini surfactant has lower CMC and better surface tension reduction ability; moreover it could form more compact and spherocylindrical micelle in the solution. These properties would be favorable for the decrease in the phase transfer energy barrier, thereby greatly accelerating the reaction rate. Meanwhile, the more compact structure of the spherocylindrical micelle formed from gemini surfactant could construct a favorable microenvironment for the formation of linear aldehyde. The comparison of the acceleration effect of the three type surfactants (monomeric surfactant CTAB (cetyltrimethylammonium bromide), gemini surfactant G(Eth), G(But), G(Hex)), G(Xyl) as well as double chain surfactant DCMAB (di(cetylmethyl)ammonium bromide) indicated that the surfactant structure had an important effect on the reaction rate. Their promotion order is DCMAB> G(Eth)≈G(But)≈G(Hex)≈G(Xyl) > CTAB.

The catalytic performance of ruthenium phosphine complexes using (1S, 2S)-DPENDS [(1S, 2S)-1, 2-diphenyl-1, 2-ethylene diamine sulfonate disodium] as a chiral modifier in the asymmetric hydrogenation of aromatic ketones was examined in a series of hydrophilic ionic liquids [RMIM]+[p-CH3 C6 H4 SO3] (R=ethyl, butyl, octyl, dodecyl). The synergistic effect between (1S, 2S)-DPENDS and KOH significantly accelerated the reaction and enhanced the enantioselectivity. An ee value of 84.8% was obtained in the asymmetric hydrogenation of acetophenone under the optimized conditions. The products were conveniently separated with cyclohexane extraction, and both the ruthenium catalyst and (1S, 2S)-DPENDS were kept in the ionic liquid and could be reused.

Alumina supported rhodium catalyst using cinchonidine as a stabilizer exhibited excellent performance in the asymmetric hydrogenation of ethyl pyruvate with the addition of quinine. Quinine as a chiral modifier can not only induce the enantioselectivity, but also greatly accelerate the reaction. Under the optimum conditions: 293 K, 7.0 MPa of hydrogen pressure and 4.6×103 mol/L of quinine concentration in THF, TOF of Rh/2(cinchonidine)-c-Al2O3 as catalyst and ee value of (R)-ethyl lactate can achieve 894 h 1 and 71.6% ee, respectively.

The hydroformylation of 1-dodecene under aqueous/organic two-phase reaction conditions with rhodium catalysts derived from BISBIS (sodium salt of sulfonated 2, 2