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DpenPhos/Rh(I)催化的β-脱氢氨基酸酯的不对称氢化反应
其他题名DpenPhos/Rh(I) Catalyzed Asymmetric Hydrogenation of Dehydro-beta-Amino Acid Esters
刘龑; 王正; 丁奎岭
2012
发表期刊化学学报
ISSN0567-7351
卷号70期号:13页码:1464-1470
其他摘要Enantiomerically pure beta-amino acids and their derivatives are very important chiral building blocks for the synthesis of beta-peptides, beta-lactams, and many important biologically active compounds. Among various methods developed for their synthesis, catalytic asymmetric hydrogenation of the corresponding dehydro-beta-amino acid esters represents one of the most efficient and environmentally benign approaches, in which the Rh(I) catalysts containing chiral phosphorous ligands play a central role. Although a variety of Rh(I) complexes of bidentate or monodentate ligands have been discovered for asymmetric hydrogenation of dehydro-beta-amino acid esters, some challenging issues still remain in terms of efficiency, enantioselectivity, and substrate scope. In the present work, a variety of Rh(I) complexes of modular monodentate phosphoramidite ligands, DpenPhos, have been systematically investigated for the asymmetric hydrogenation of (E)- or (Z)-beta-substituted dehydro-beta-amino acid esters. It was found that the presence of a N-H moiety in the phosphoramidite ligand is critically important for achieving high activity of the catalysis. Both (Z)- and (E)-geometrical isomers of the beta-acetamido acrylic acid esters can be hydrogenated in the presence of DpenPhos/Rh(I) catalysts to form the same enantiomers, albeit slightly different conditions were required to attain optimal enantioselectivities. (R,R)-3k/Rh(I) (1 mol%) was disclosed to be optimal for the hydrogenation of (E)-beta-alkyl substituted dehydro-beta-amino acid esters in dichloromethane under a relatively low pressure of hydrogen (0.5 MPa), affording the corresponding beta-amino acid esters with 92%-96% ee. The reaction still proceeded smoothly without significant sacrifice of activity or enantioselectivity either at a catalyst loading of 0.2 mol% or 0.1 MPa pressure of H-2. For the hydrogenation of more challenging (Z)-beta-alkyl or aryl substituted dehydro-beta-amino acid esters, (R,R)-3l/Rh(I) in combination with the dichloromethane/isopropanol (V/V=2/1) mixed solvent system turned out to be the best in terms of enantioselectivity and catalytic activity, giving a variety of beta-alkyl or aryl substituted beta-amino acid esters in >99% yields with excellent optical purities (92%-98% ee).
学科领域金属有机化学
部门归属中科院上海有机化学研究所
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收录类别SCI
语种中文
文献类型期刊论文
条目标识符http://ir.sioc.ac.cn/handle/331003/28113
专题金属有机化学国家重点实验室
通讯作者丁奎岭
推荐引用方式
GB/T 7714
刘龑,王正,丁奎岭. DpenPhos/Rh(I)催化的β-脱氢氨基酸酯的不对称氢化反应[J]. 化学学报,2012,70(13):1464-1470.
APA 刘龑,王正,&丁奎岭.(2012).DpenPhos/Rh(I)催化的β-脱氢氨基酸酯的不对称氢化反应.化学学报,70(13),1464-1470.
MLA 刘龑,et al."DpenPhos/Rh(I)催化的β-脱氢氨基酸酯的不对称氢化反应".化学学报 70.13(2012):1464-1470.
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