New hydroformylation rhodium catalysts with dithiolate chiral ligands

Q4 Chemical Engineering

分子催化 Pub Date : 1994-11-27 DOI:10.1016/S0304-5102(94)87036-5

A.M. Masdeu, A. Orejón, A. Ruiz, S. Castillón, C. Claver

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引用次数: 25

Abstract

Asymmetric hydroformylation of styrene is performed using the bridge dithiolate chiral rhodium complexes [Rh₂(μ-(−)-DIOS)(cod)₂]_n n=2 (1); and n=1 (2); ((−)-DIOS: 2,3-O-isopropylidene-1,4-dithiO-L-threitol and cod: 1,5-cyclooctadiene) as catalyst precursors. The catalytic system 1 provides high conversion in the corresponding aldehydes (100% at 30 bar, 65°C) with a selectivity in 2-phenylpropanal of 64%. Addition of PPh₃ to the catalytic system 1 increases the selectivity in 2-phenylpropanal to 91 % in the same conditions. Although the ee's obtained using 1 were low (3–5%), the addition of a chiral phosphine, (+)-DIOP ((2S,3S)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis (diphenylphosphino)butane), improves the ee in (S)-2-phenylpropanal to 17%. However the addition of (−)-DIOP gives a lower ee (3% (S)). Comparative results were obtained using 2 as catalyst precursor indicating that similar species were formed during catalytic cycle.

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新型二硫代酸酯手性配体氢甲酰化铑催化剂

采用桥式二硫代手性铑配合物[Rh2(μ-(−)- dios)(cod)2]n n=2(1)进行苯乙烯的不对称氢甲酰化反应;n=1 (2);(−)-DIOS: 2,3- o -异丙烯-1,4-二硫- l -苏糖醇和cod: 1,5-环二烯)作为催化剂前驱体。催化系统1在相应的醛中提供高转化率(在30巴，65℃下100%)，对2-苯丙醛的选择性为64%。在相同条件下，在催化体系1中加入PPh3将2-苯丙醛的选择性提高到91%。虽然用1得到的ee很低(3-5%)，但加入手性膦(+)-DIOP ((2S,3S)-2,3- o -异丙烯-2,3-二羟基-1,4-双(二苯基膦)丁烷)后，(S)-2-苯基丙烷的ee提高到17%。然而，(−)-DIOP的加入使ee较低(3% (S))。以2为催化剂前驱体的对比结果表明，在催化循环过程中形成了相似的物质。

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来源期刊

分子催化 Chemical Engineering-Catalysis

CiteScore

1.50

自引率

0.00%

发文量

2959

期刊介绍： Journal of Molecular Catalysis (China) is a bimonthly journal, founded in 1987. It is a bimonthly journal, founded in 1987, sponsored by Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, under the supervision of Chinese Academy of Sciences, and published by Science Publishing House, which is a scholarly journal openly circulated both at home and abroad. The journal mainly reports the latest progress and research results on molecular catalysis. It contains academic papers, research briefs, research reports and progress reviews. The content focuses on coordination catalysis, enzyme catalysis, light-ribbed catalysis, stereochemistry in catalysis, catalytic reaction mechanism and kinetics, the study of catalyst surface states and the application of quantum chemistry in catalysis. We also provide contributions on the activation, deactivation and regeneration of homogeneous catalysts, solidified homogeneous catalysts and solidified enzyme catalysts in industrial catalytic processes, as well as on the optimisation and characterisation of catalysts for new catalytic processes. The main target readers are scientists and postgraduates working in catalysis in research institutes, industrial and mining enterprises, as well as teachers and students of chemistry and chemical engineering departments in colleges and universities. Contributions from related professionals are welcome.