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2012 , Vol. 70 >Issue 13: 1464 - 1470

DOI: https://doi.org/10.6023/A12030050

研究论文

DpenPhos/Rh(I)催化的β-脱氢氨基酸酯的不对称氢化反应

  • 刘龑 ,
  • 王正 ,
  • 丁奎岭
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  • 中国科学院上海有机化学研究所 金属有机化学国家重点实验室 上海 200032

收稿日期: 2012-03-23

  网络出版日期: 2012-05-03

基金资助

项目受国家自然科学基金(Nos. 21172237, 21121062, 21032007)和“973计划”(No. 2010CB833300)资助.

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DpenPhos/Rh(I) Catalyzed Asymmetric Hydrogenation of Dehydro-β-Amino Acid Esters

  • Liu Yan ,
  • Wang Zheng ,
  • Ding Kuiling
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  • State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Received date: 2012-03-23

  Online published: 2012-05-03

Supported by

Project supported by the National Natural Science Foundation of China (Nos. 21172237, 21121062, 21032007) and Major Basic Research Program of China (No. 2010CB833300).

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摘要

本文研究了一类结构可调手性单齿亚磷酰胺配体DpenPhos在Rh(I)催化的E和Z型β-脱氢氨基酸酯的不对称催化氢化反应中的应用. 经过系统的反应条件和配体结构优化, 发现N原子上含有H的亚磷酰胺配体与Rh(I)形成的催化剂通常比N原子上不含H的配体表现出更高的反应活性. 在E型β-脱氢氨基酸酯的不对称氢化反应中, 催化剂(R,R)- 3k/Rh(I)表现突出, 可以实现底物的常压催化氢化, 取得了92%～96%的对映选择性, 催化剂用量可降低至0.2 mol%; 对于Z型β-脱氢氨基酸酯的不对称氢化反应, 则(R,R)-3l/Rh(I)为最优催化剂, 可以获得92%～98% ee值的氢化产物, 特别是对于β-芳基取代衍生物的氢化反应, 相应氢化产物的ee值可以达到96%～98%. 该类催化剂为天然或非天然光学活性β氨基酸的合成提供了一个简便、高效的方法.

关键词： 不对称催化; 氢化; 单磷配体; 亚磷酰胺; 铑; β-脱氢氨基酸甲酯

本文引用格式

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 . DOI: 10.6023/A12030050

Abstract

Enantiomerically pure β-amino acids and their derivatives are very important chiral building blocks for the synthesis of β-peptides, β-lactams, and many important biologically active compounds. Among various methods developed for their synthesis, catalytic asymmetric hydrogenation of the corresponding dehydro-β-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-β-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)-β-substituted dehydro-β-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 β-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)-β-alkyl substituted dehydro-β-amino acid esters in dichloromethane under a relatively low pressure of hydrogen (0.5 MPa), affording the corresponding β-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 H2. For the hydrogenation of more challenging (Z)-β-alkyl or aryl substituted dehydro-β-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 β-alkyl or aryl substituted β-amino acid esters in ＞99% yields with excellent optical purities (92%-98% ee).

Key words： asymmetric catalysis; hydrogenation; monodentate ligand; phosphoramidite; rhodium; dehydro-β-amino acid ester

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