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 hydroformylation of long-chain olefins catalyzed by the water soluble rhodium complex, RhCl (CO) (TPPTS) 2, were studied in aqueous/organic biphasic system containing cationic surfactants. The addition of TPPDS as a modifier dramatically increased the regioselectivity of olefin hydroformylation. A synergistic effect of TPPTS and TPPDS on the regioselectivity was observed. The ratio of linear/branched aldehyde rose from 6.5 (without TPPDS) to 22.3 ([TPPTS]/[TPPDS]=2:1). The steric structure of hydrophilic group in the cationic surfactants exhibited an important influence on the regioselectivity. The hydrophilic group with a small steric volume was favorable for the formation of linear aldehyde. It was found that when the alkyl chain length of the higher olefin and that of the cationic surfactant were comparable (matching size), the regioselectivity for linear aldehyde was outstandingly high.

Hydroformylation of 1-dodecene catalyzed by water-soluble rhodium-phosphine complex, RhCl (CO) (TPPTS)2 (TPPTS: P(m-C6 H4 SO3 Na)), in the presence of various mixed micelles was investigated. When either an anionic surfactant sodium dodecyl sulfate (SDS) or dodecylbenzonesulphonate (DBS), a nonionic surfactant Triton X-100 or Brij 35, or alcohol was added into cationic surfactant cetyl pyrindium bromide (CPB) solution, a mixed micelle formed. The decrease in critical micelle concentration (CMC) and the increase in solubilization of 1-dodecene in the mixed micelle were observed. Hydroformylation of 1-dodecene exhibited higher conversion and higher regioselectivity in the mixed micellar solution than in the single micelle of CPB. The synergistic mechanism of two different surfactants was discussed.

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.

1-Dodecene hydroformylation catalyzed by water-soluble rhodium complex, RhCl (CO) (TPPTS) [TPPTS: P (m-C6 H4 SO3 Na)3], in the presence of surfactants and alcoholic solvents was studied. The results indicated that the hydroformylation in biphasic catalytic system occurred in the interface of aqueousrorganic phases. The formation of micelle was not only favorable for the reaction acceleration, but also favorable for the increase of linear aldehyde ratio in products. The key factor of the enhancement of reaction rate was the richness of rhodium catalyst in the interlayer with the static electricity attraction between active rhodium anion species and cationic end of surfactant.