硫脲催化剂催化硝基烯烃的Michael加成反应的研究进展

靠氢键作用结合的硫脲催化剂因其良好的催化活性而受到广泛关注,被应用于各种不对称Michael加成反应中。本文主要介绍了硫脲催化剂在催化硝基烯烃的Michael加成反应中的研究现状,并对其应用前景及发展趋势进行了展望。     

Michael加成反应的研究进展

综述了微波辐射、超声辐射、催化不对称合成以及固相反应等在Michael加成反应中的应用，总结了Michael加成反应的研究进展，并对今后的研究方向提出了建议。     

不对称Michael加成反应研究进展

随着有机小分子催化不对称有机合成反应的发展,人们设计出了大量的手性有机小分子催化剂并对于有机小分子催化的不对称Michael加成也进行了大量的研究。本文综述了近年来国内外不同研究小组对不对称Michael加成的研究进展,并对不同催化剂在不对称Michael加成反应中的应用进行了简单的评述。     

手性伯胺催化剂催化Michael加成反应的研究进展

在许多不对称有机反应中,手性伯胺催化剂已被证实是一种高效的催化剂,被广泛应用于各种Michael加成反应中。Michel加成是有机合成中构建碳一碳键的重要反应之一,本文综述了近年来手性伯胺催化剂在Michael加成反应中的研究新进展。     

不对称Michael加成反应的研究进展

综述了近年来催化不对称Michael加成反应的新方法,包括新手性胺催化的不对称加成反应、手性金属配合物催化的反应、手性冠醚催化的反应及其他催化反应.     

水相中新型有机小分子催化下的不对称Michael反应

合成了迄今未有报道的新型有机催化剂,并研究了在该有机催化下水相中不同类型的酮与各种硝基烯烃的反应。研究表明：水相中进行的Michael加成反应在合成的新型有机催化剂的作用下,有较高的产率（最高达93%）和较好的对映选择性,ee值最高达96%。     

硝基烯烃与丙二酸酯的Michael加成反应研究

以β-CF_3-β-(3-吲哚)硝基烯烃衍生物和丙二酸酯为反应起始原料,在碳酸铯碱性条件下,用甲苯作为反应溶剂,于35℃下搅拌反应,实现了β-CF_3-β-(3-吲哚)硝基烯烃衍生物与丙二酸酯的Michael加成反应。通过对碱、反应溶剂、碱的用量、底物浓度和反应温度等因素的考察,确定了反应的最优条件。然后,在最优条件下,实现了不同结构的β-CF_3-β-(3-吲哚)硝基烯烃与丙二酸酯的Michael加成反应,以最高95%的收率获得了既含三氟甲基又含吲哚片段的γ-硝基丁酸酯,其结构均经过~1HNMR、~(13)CNMR、ESI-HRMS和IR确证。     

磷酸锌钠负载KF催化Michael加成反应

以磷酸锌钠负载KF为催化剂,催化乙酰乙酸乙酯与丙烯腈进行Michael加成反应.用熔点测定仪、IR、GCMS、1H-NMR表征了加成产物,产物的总产率为81.8%.实验结果表明,KF/NaZnPO4是一种催化α,β不饱和共轭体系和含有活泼亚甲基化合物反应的良好催化剂,该反应可在温和的条件下高效地进行,产品产率高,纯度好,操作和后处理简单方便.     

有机小分子催化剂在硝基烯类化合物与醛酮的不对称Michael加成反应中的应用探究

有机小分子催化剂以其相对廉价易得、无金属参与、对环境污染小、催化活性良好的优势,受到许多化学家的关注。在醛、酮与硝基烯类的不对称Michael加成反应中也得到成功的应用。本文综述近几年来,硝基烯类化合物参与的与醛、酮不对称Michael加成反应的各类α,β-不饱和有机底物以及所用到的有机小分子催化剂。总结其优缺点,以期待能够更加广泛的催化剂被研制出来。     

纳米二氧化硅催化剂催化Michael加成反应

脱水活化后的纳米二氧化硅颗粒能有效催化Michael加成反应,研究了不同温度及六甲基二硅氮烷(HMDS)处理改变二氧化硅表面性质后催化剂的催化性能改变。结果表明,随着热处理温度的升高,二氧化硅催化活性降低;HMDS能够覆盖其表面的单独硅羟基,从而降低二氧化硅催化活性。研究表明,二氧化硅表面的硅羟基是催化活性中心,催化活性与硅羟基浓度相关。不同溶剂对反应活性影响明显,DMF为反应的最佳溶剂,反应收率最高可达71%。     

Highly Efficient Amine Organocatalysts Based on Bispidine for the Asymmetric Michael Addition of Ketones to Nitroolefins

A highly diastereoselective and enantioselective Michael addition of cyclohexanone, acetone and other ketones to nitroolefins was developed by the use of an amine organocatalyst based on bispidine. Additionally, a theoretical study of transition structures revealed that this bispidine‐based primary‐secondary amine catalyst could serve through an enamine intermediate and H‐bond interaction, which was important for the reactivity and selectivity of this reaction.     

A Chiral Functionalized Salt‐Catalyzed Asymmetric Michael Addition of Ketones to Nitroolefins

The chiral functionalized salt catalysis, which differs from the known enzyme‐ and transition metal‐based methods, has been successfully developed to carry out the Michael addition of ketones to nitroolefins. Chiral anion salt (type I ), chiral cation salt (type II ), or chiral anion‐chiral cation salt (type III ) could be expected to be remarkably effective catalysts and afford the corresponding chemically and optically pure Michael addition adducts. A primary amine group activating the ketone during salt catalysis was their obvious and common property. Based on preliminary experimental investigations and previous reports on primary amine catalysis, a reaction pathway via imine, enamine, iminium ion to imine was proposed.     

A Highly Selective,Polymer‐Supported Organocatalyst for Michael Additions with Enzyme‐Like Behavior

A polymer‐supported α,α‐diarylprolinol silyl ether displays catalytic activity and enantioselectivity comparable to the best homogeneous catalysts in the Michael addition of aldehydes to nitroolefins. Above all, the combination of polymer backbone, triazole linker, and catalytic unit confers to it an unprecedented substrate selectivity in favor of linear, short‐chain aldehydes.     

Stereocontrolled Construction of Quaternary Stereocenters by Inter‐ and Intramolecular Nitro‐Michael Additions Catalyzed by Bifunctional Thioureas

A highly diastereo‐ and enantioselective conjugate addition of β‐keto esters to nitroolefins, catalyzed by a chiral thiourea prepared from L ‐valine is described. The formation of two contiguous tertiary and quaternary stereocenters occurs in high yield and excellent diastereo‐ and enantioselection with only 2 mol% of catalyst loading. The reaction is general and different β‐keto esters and aryl‐ and alkylnitroolefins have been tested. The same catalyst has been used to promote the first intramolecular conjugate addition leading to the cyclic adduct in moderate diastereoselectivity and good enantioselectivity.     

钛,锆,铪取代的膦叶立德的合成及应用

简介了ⅣＢ族金属－钛、锆和铪取代的膦叶立德的各种合成方法及它们与酮、醇和一氧化碳的反应。     

Primary Amine‐Thioureas with Improved Catalytic Properties for “Difficult” Michael Reactions: Efficient Organocatalytic Syntheses of (S)‐Baclofen, (R)‐Baclofen and (S)‐Phenibut

Among the class of primary amine‐thioureas based on tert‐butyl esters of α‐amino acids, the most efficient organocatalyst for “difficult” Michael reactions was identified. The derivative based on (S)‐di‐tert‐butyl aspartate and (1R,2R)‐diphenylethylenediamine provided the products of the reaction between aryl methyl ketones and nitroolefins in excellent yields and enantioselectivities. In addition, this new catalyst can be used at low catalyst loading (5 mol%). The utility of this methodology was highlighted by the efficient synthesis of (S)‐baclofen, (R)‐baclofen and (S)‐phenibut.     

2-硫代-4-噻唑酮与查尔酮的无溶剂Michael加成反应

以查尔酮和2-硫代-4-噻唑酮为原料,在NaOH存在下无溶剂室温研磨反应,非常方便合成了系列未见文献报道的Michael加成产物.该方法具有反应条件温和、操作简单和产率较高等优点,并通过IR、HNMR、MS和元素分析确证产物的结构.