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学科主题: 金属有机化学
题名: 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
作者: 刘龑 ; 王正 ; 丁奎岭
通讯作者: 丁奎岭
刊名: 化学学报
发表日期: 2012-01-01T00:00:00Z
卷: 70, 期:13, 页:1464-1470
收录类别: SCI
部门归属: 中科院上海有机化学研究所
英文摘要: 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).
语种: 中文
相关网址: 查看原文
内容类型: 期刊论文
URI标识: http://ir.sioc.ac.cn/handle/331003/28113
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Recommended Citation:
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.
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