Evaluation of calix[4]arene-based chiral diphosphite ligands in Rh-catalyzed asymmetric hydrogenation of simple dehydroamino acid derivatives

被引：15

作者：

Liu, Shasha ^{[2
]}

Sandoval, Christian A. ^{[1
]}

机构：

[1] Chinese Acad Sci, Shanghai Inst Organ Chem, Shanghai 200032, Peoples R China

[2] Tianjin Univ, Dept Chem, Coll Sci, Tianjin 300072, Peoples R China

来源：

JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL | 2010年 / 325卷 / 1-2期

关键词：

Asymmetric catalysis; Homogeneous catalysis; Hydrogenation; Calixarene; Phosphite ligand; Rhodium; PHOSPHORUS LIGANDS; UPPER RIM; COMPLEXES; HYDROFORMYLATION; MECHANISM; PHOSPHITES; MIXTURES; PALLADIUM; STATE; NMR;

D O I：

10.1016/j.molcata.2010.03.034

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The calix[4]arene framework was readily modified to generate a number of chiral BINOL-based diphosphite ligands (3) capable of forming in situ Rh-complexes which catalyzed the asymmetric hydrogenation of model substrates methyl-(Z)-2-(acetamido)acrylate (1a) and methyl-(Z)-2-(acetamido)cinnamate (1b). The (S,S)-catalyst generated the (R)-product. Upper rim (R-1) and 1,3-O-alkylation (R-2) substitution on the calixarene strongly influenced catalyst activity and chiral induction. Optimum results were obtained when RI was -C(CH3)(3) and R-2 was -CH2CH2CH3 (3b). Under optimized conditions, 3b hydrogenated la and 1b in 98 and 96% ee, respectively. Overall, better catalyst performance was observed for "locked" cone-conformers of 3, with higher activity evident for the less sterically hindered 1a (TOF up to 1300h(-1) at P(H-2) = 5 atm). (C) 2010 Elsevier B.V. All rights reserved.

引用

页码：65 / 72

页数：8

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