Solvent-free asymmetric olefin hydroformylation catalyzed by highly cross-linked polystyrene-supported (R,S)-BINAPHOS-Rh(I) complex
Solvent-free asymmetric olefin hydroformylation catalyzed by highly cross-linked polystyrene-supported (R,S)-BINAPHOS-Rh(I) complex
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DOI：
10.1021/ja034447u
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发表时间：
2003-07-16
影响因子：
15
通讯作者：
Hiyama, T
中科院分区：
文献类型：
--
作者：
Shibahara, F;Nozaki, K;Hiyama, T
使用共价锚定在高度交联聚苯乙烯载体上的(RS)-BINAPHOS-Rh(I)催化剂，在没有有机溶剂的情况下进行了烯烃的不对称氢甲酰化反应。气态底物顺式-2-丁烯在固定床的间歇式反应器中，经H-2 （12atm）和CO （12atm）处理，产生了100%区域选择性和82% ee的(S)-2-甲基丁醛。该聚合物负载催化剂适用于连续汽流塔反应器，3,3,3-三氟丙烯以95/5的等/正比和90%的ee转化为(S)-2-三氟甲基丙烷。通过超临界co2流塔式反应器注入挥发性较低的烯烃，如苯乙烯、醋酸乙烯、1-烯烃和氟化烯烃，成功地转化为相应的高ee值的异醛。一系列烯烃的连续注入实现了烯烃库向光学活性醛库的转化。
Using an (RS)-BINAPHOS-Rh(I) catalyst that is covalently anchored to a highly cross-linked polystyrene support, asymmetric hydroformylation of olefins was performed in the absence of organic solvents. The reaction of cis-2-butene, a gaseous substrate, provided (S)-2-methylbutanal with 100% regioselectivity and 82% ee upon treatment with H-2 (12 atm) and CO (12 atm) in a batchwise reactor equipped with a fixed bed. The polymer-supported catalyst was applicable to a continuous vapor-flow column reactor, and thus, 3,3,3-trifluoropropene was converted into (S)-2-trifluoromethylpropanal with an iso/normal ratio of 95/5 and 90% ee. Less volatile olefins, such as styrene, vinyl acetate, 1-alkenes, and fluorinated alkenes, were successfully converted into the corresponding isoaldehydes with high ee values, when they were injected through a supercritical CO2-flow column reactor. Successive injection of a series of olefins realized the conversion of an olefin library into an optically active aldehyde library.