Synthesis and catalytic activity of new supported rhodium(I) complexes for the enantioselective hydrogenation of methyl-(Z)-α-N-acetamidocinnamate
Synthesis and catalytic activity of new supported rhodium(I) complexes for the enantioselective hydrogenation of methyl-(Z)-α-N-acetamidocinnamate
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DOI：
10.1016/s1381-1169(01)00424-1
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发表时间：
2002-03-11
影响因子：
--
通讯作者：
Nobile, CF
中科院分区：
文献类型：
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作者：
Mastrorilli, P;Rizzuti, A;Nobile, CF
通过(cod)Rh(AAEMA)与(+)-diop在-80℃下反应，得到聚合性铑络合物[(+)-diopRh(AAEMA)](AAEMA(-)：配体2-(乙酰乙酰氧基)-甲基丙烯酸乙酯的去质子化形式)。通过[(+)-diopRh(AAEMA)l与NN-二甲基丙烯酰胺和N,N'-亚甲基-双丙烯酰胺的共聚或通过[(+)-diopRhCl](2)与适当制备的聚(β-酮酯)反应获得了负载的手性配合物。使用均相催化剂或其非均相类似物进行的催化测试：证明在甲基-(Z)-α-N-乙酰氨基肉桂酸酯的对映选择性氢化中具有活性，生成(S)-苯丙氨酸甲酯，ee高达67%。 (C) 2002 Elsevier Science B.V. 保留所有权利。
The polymerizable rhodium complex [(+)-diopRh(AAEMA)] (AAEMA(-): deprotonated form of the ligand 2-(acetoacetoxy)-ethylmethacrylate) was obtained by reaction of (cod)Rh(AAEMA) with (+)-diop at -80 degreesC. Supported chiral complexes have been obtained by copolymerization of [(+)-diopRh(AAEMA)l with NN-dimethylacrylamide and N,N'-methylene-bisacrylamide or by reaction of [(+)-diopRhCl](2) with an opportunely prepared: poly(beta-ketoesterate). Catalytic tests carried out with the homogeneous catalyst or with both its heterogeneous analogues:proved to be active in the enantioselective hydrogenation of methyl-(Z)-alpha-N-acetamidocinnamate yielding (S)-phenylalanine methylester with ee's up to 67%. (C) 2002 Elsevier Science B.V. All rights reserved.