Synthesis, Crystal Structures and Catalysis of Dinuclear Cd(Ⅱ) Complexes Bridged by Unusual (N,O,O′)-Coordinated α-Amino Acids

高等学校化学研究 ›› 2012, Vol. 28 ›› Issue (1): 73-78.

Synthesis, Crystal Structures and Catalysis of Dinuclear Cd(Ⅱ) Complexes Bridged by Unusual (N,O,O′)-Coordinated α-Amino Acids

DENG Dong-sheng^1,2, WANG Li^1*, PEI Ya-mei¹, FENG Lu², LIU Chang-lin¹

1. Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, School of Chemistry, Central China Normal University, Wuhan 430079, P. R. China;
2. College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, P. R. China

收稿日期:2011-02-25 修回日期:2011-03-24 出版日期:2012-01-25 发布日期:2011-12-27
基金资助:
Supported by the National Natural Science Foundation of China(No.21001047) and the Self-determined Research Funds of Central China Normal University from the Colleges' Basic Research and Operation of Ministry of Education, China(No. CCNU10A01010).

Synthesis, Crystal Structures and Catalysis of Dinuclear Cd(Ⅱ) Complexes Bridged by Unusual (N,O,O′)-Coordinated α-Amino Acids

DENG Dong-sheng^1,2, WANG Li^1*, PEI Ya-mei¹, FENG Lu², LIU Chang-lin¹

1. Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, School of Chemistry, Central China Normal University, Wuhan 430079, P. R. China;
2. College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, P. R. China

Received:2011-02-25 Revised:2011-03-24 Online:2012-01-25 Published:2011-12-27
Contact: Li Wang E-mail:wl_928@mail.ccnu.edu.cn
Supported by:
Supported by the National Natural Science Foundation of China(No.21001047) and the Self-determined Research Funds of Central China Normal University from the Colleges' Basic Research and Operation of Ministry of Education, China(No. CCNU10A01010).

摘要/Abstract

摘要： Four dinuclear amino acid cadmium(Ⅱ) complexes [Cd₂(tren)₂(dl-alaninato)](ClO₄)₃·H₂O(Ⅰ), [Cd₂(tren)₂·(l-alaninato)](ClO₄)₃·H₂O(Ⅱ), [Cd₂(tren)₂(dl-phenylalaninato)](ClO₄)₃(Ⅲ) and [Cd₂(tren)₂(l-phenylalaninato)]· (ClO₄)₃(Ⅳ), constructed from mixed ligands of tris(2-aminoethyl)amine(tren) and racemic or natural amino acids( amino acids=dl- or l-alanine, and dl- or l-phenylalanine), have been synthesized and characterized by X-ray crystallography. The structural analysis of complexes Ⅰ and Ⅲ reveals that the cadmium centers are coordinated by one tren ligand and one amino acid molecule with the unusual (N,O,O′)-bridged mode, resulting in asymmetric chromophores of CdN₄O and CdN₅O in complex Ⅰ, CdN₄O₂ and CdN₅O in complex Ⅲ, respectively. The utility of the four complexes as efficient water-compatible Lewis acid catalysts for the direct aldol reaction in water was examined. The reaction proceeded smoothly to afford the corresponding β-hydroxy ketones in up to 99% yield. Moreover, the diastereoselectivity of the reaction favors the formation of the syn-isomers.

关键词: Dinuclear cadmium(Ⅱ) complex, Amino acid, Aldol reaction

Abstract: Four dinuclear amino acid cadmium(Ⅱ) complexes [Cd₂(tren)₂(dl-alaninato)](ClO₄)₃·H₂O(Ⅰ), [Cd₂(tren)₂·(l-alaninato)](ClO₄)₃·H₂O(Ⅱ), [Cd₂(tren)₂(dl-phenylalaninato)](ClO₄)₃(Ⅲ) and [Cd₂(tren)₂(l-phenylalaninato)]· (ClO₄)₃(Ⅳ), constructed from mixed ligands of tris(2-aminoethyl)amine(tren) and racemic or natural amino acids( amino acids=dl- or l-alanine, and dl- or l-phenylalanine), have been synthesized and characterized by X-ray crystallography. The structural analysis of complexes Ⅰ and Ⅲ reveals that the cadmium centers are coordinated by one tren ligand and one amino acid molecule with the unusual (N,O,O′)-bridged mode, resulting in asymmetric chromophores of CdN₄O and CdN₅O in complex Ⅰ, CdN₄O₂ and CdN₅O in complex Ⅲ, respectively. The utility of the four complexes as efficient water-compatible Lewis acid catalysts for the direct aldol reaction in water was examined. The reaction proceeded smoothly to afford the corresponding β-hydroxy ketones in up to 99% yield. Moreover, the diastereoselectivity of the reaction favors the formation of the syn-isomers.

Key words: Dinuclear cadmium(Ⅱ) complex, Amino acid, Aldol reaction

DENG Dong-sheng, WANG Li, PEI Ya-mei, FENG Lu, LIU Chang-lin. Synthesis, Crystal Structures and Catalysis of Dinuclear Cd(Ⅱ) Complexes Bridged by Unusual (N,O,O′)-Coordinated α-Amino Acids[J]. 高等学校化学研究, 2012, 28(1): 73-78.

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Synthesis, Crystal Structures and Catalysis of Dinuclear Cd(Ⅱ) Complexes Bridged by Unusual (N,O,O′)-Coordinated α-Amino Acids

Synthesis, Crystal Structures and Catalysis of Dinuclear Cd(Ⅱ) Complexes Bridged by Unusual (N,O,O′)-Coordinated α-Amino Acids

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