一个新的Cu(II)-二胺配合物催化的Henry反应

doi:10.3724/SP.J.1095.2014.30284

摘要/Abstract

摘要： 研究了L-脯氨酸制得的C2-对称二胺，与醋酸铜形成新的配合物，催化各种醛与硝基烷烃间的Henry反应。考察了反应温度、溶剂和催化剂用量对收率和反应速率的影响。研究结果表明，在室温下，以乙醇作为反应溶剂时，摩尔分数10%的二胺醋酸铜配合物能够有效地催化醛与硝基甲烷反应，生成相应的β-硝基醇，收率为60%~92%。醛与硝基乙烷的Henry反应产物具有非对映立体选择性。芳香醛参与Henry反应产物的非对映选择性高达24∶1，但脂肪醛为底物时，此催化剂对Henry反应的非对映选择性不明显。

关键词: Henry反应, C2-对称二胺Cu(Ⅱ)配合物, 催化作用, 双齿配体

Abstract: A new copper acetate complex derived from C2-symmetric diamine, which can be easily prepared from L-proline, was developed and used as an efficient catalyst in Henry reaction between various aldehydes and nitroalkanes. The results demonstrate that the reaction temperature, solvents and catalyst loadings have considerably effects on both yields and reaction rates. The yields are 60%~92% in optimal reaction conditions:at room temperature, ethanol as solvent, 10% molar fraction of catalyst loading. All aldehydes react efficiently with tested nitroalkanes to produce corresponding β-nitroalcohols. When aromatic aldehydes react with nitroethane, excellent diastereoselectivity can be obtained. However, diastereoselectivity is modest in the reaction of aliphatic acetaldehyde.

Key words: Henry reaction, copper acetate, C2-symmetric diamine, bidentate ligand

中图分类号:

O625

苏策, 夏淑娇, 常文武, 韩丽娟. 一个新的Cu(II)-二胺配合物催化的Henry反应[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.30284.

SU Ce*, XIA Shujiao, CHANG Wenwu, HAN Lijuan. A New Cu(II)-diamine Complex Catalyzed Henry Reaction[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30284.

参考文献

[1] Luzzio F A. The Henry Reaction:Recent Examples[J]. Tetrahedron,2001,57(6):915-946.

[2] Ono N. The Nitro Group in Organic Synthesis[M]. Wiley-VCH,New York,USA,2001.

[3] Tosaki S,Hara K,Gnanadesikan V,et al. Mixed La-Li Heterobimetallic Complexes for Tertiary Nitroaldol Resolution[J]. J Am Chem Soc,2006,128(36):11776-11777.

[4] Evans D A,Seidel D,Rueping M,et al. A New Copper Acetate-Bis(oxazoline)-Catalyzed, Enantioselective Henry Reaction[J]. J Am Chem Soc,2003,125(42):12692-12693.

[5] Lang K,Park J,Hong S. Development of Bifunctional Aza-Bis(oxazoline) Copper Catalysts for Enantioselective Henry Reaction[J]. J Org Chem,2010,75(19):6424-6435.

[6] Subba R B,George J. Enantioselective Henry Reaction Catalyzed by a Copper(Ⅱ)-BOX Complex[J]. Tetrahedron:Asymmetry,2011,22(11):1169-1175.

[7] Constable E C,Zhang G,Housecroft C E,et al. In Search of Enantioselective Catalysts for the Henry Reaction:Are Two Metal Centres Better than One[J]. New J Chem,2009,33(5):1064-1069.

[8] Steurer M,Bolm C. Synthesis of Amino-Functionalized Sulfonimidamides and Their Application in the Enantioselective Henry Reaction[J]. J Org Chem,2010,75(10):3301-3310.

[9] Kim H Y,Oh K. Brucine-Derived Amino Alcohol Catalyzed Asymmetric Henry Reaction:an Orthogonal Enantio-Selectivity Approach[J]. Org Lett,2009,11(24):5682-5685.

[10] Maheswaran H,Prasanth K L,Krishna G G,et al. Enantioselective Nitroaldol(Henry) Reaction Using Copper(Ⅱ) Complexes of (-)-Sparteine[J]. Chem Commun,2006,39:4066-4068.

[11] Kureshy R I,Das A,Khan N H,et al. Cu(Ⅱ)-Macrocylic [H4] Salen Catalyzed Asymmetric Nitroaldol Reaction and Its Application in the Synthesis of α1-Adrenergic Receptor Agonist (R)-Phenylephrine[J]. ACS Catal,2011,1(11):1529-1535.

[12] Dhahagani K,Rajesh J,Kannan R,et al. Asymmetric Henry Reaction of Aldehydes Catalyzed by Recyclable an MCM-41 Supported Copper(Ⅱ) Salen Complex[J]. Tetrahedron:Asymmetry,2011,22(8):857-865.

[13] White J D,Shaw S. A New Catalyst for The Asymmetric Henry Reaction:Synthesis of β-Nitroethanols in High Enantiomeric Excess[J]. Org Lett,2012,14(24):6270-6273.

[14] Arai T,Takashita R,Endo Y,et al. Asymmetric Syn-Selective Henry Reaction Catalyzed by the Sulfonyldiamine-CuCl-Pyridine System[J]. J Org Chem,2008,73(13):4903-4906.

[15] Tanaka K,Hachiken S. Enantioselective Henry Reaction Catalyzed by Trianglamine-Cu(OAc)2 Complex under Solvent-free Conditions[J]. Tetrahedron Lett,2008,49(16):2533-2536.

[16] Arai T,Watanabe M,Fujiwara A,et al. Direct Monitoring of the Asymmetric Induction of Solid-Phase Catalysis Using Circular Dichroism:Diamine-CuI-Catalyzed Asymmetric Henry Reaction[J]. Angew Chem Int Ed,2006,45(36):5978-5981.

[17] Nakamura D,Kakiuchi K,Koga K,et al. Design and Synthesis of Novel C2-Symmetric Chiral Piperazines and an Application to Asymmetric Acylation of σ-Symmetric 1,2-Diols[J]. Org Lett,2006,8(26):6139-6142.

[18] Bulut A,Aslan A,Dogan O. Catalytic Asymmetric Nitroaldol(Henry) Reaction with a Zinc-Fam catalyst[J]. J Org Chem,2008,73(18):7373-7375.

[19] Noole A,Lippur K,Metsala A,et al. Enantioselective Henry Reaction Catalyzed by CuⅡ Salt and Bipiperidine[J]. J Org Chem,2010,75(4):1313-1316.

[20] Zhou C,Zhou Y,Wang Z. Henry Reaction in Aqueous Media:Chemoselective Addition of Aldehydes[J]. Chinese Chem Lett,2003,14(4):355-358.

[21] Blay G,Domingo L R,Hern ndez-Olmos V,et al. New Highly Asymmetric Henry Reaction Catalyzed by CuⅡ and a C1-Symmetric Aminopyridine Ligand, and Its Application to the Synthesis of Miconazole[J]. Chem Eur J,2008,14(15):4725-4730.

[22] Selvakumar S,Sivasankarana D,Singh V K. Enantioselective Henry Reaction Catalyzed by C2-Symmetric Chiral Diamine Copper(Ⅱ) Complex[J]. Org Biomol Chem,2009,7(15):3156-3162.