丙二酸亚异丙酯的双Michael加成

丙二酸亚异丙酯(Isoproplidene malonate orMeidrum's acid)是一种有用的有机合成中间体。最近,陈振初等报道了丙二酸亚异丙酯和某些亲电烯烃(CH_2=CHCO_2Et,CH_2=CHCN,CH_2=CHCOCH_3,EtO_2CCH=CHCO_2Et)     

Michael Addition Reaction of Fluorinated Nitro Compounds

The Michael addition reactions of fluorinated nitro compounds with electron deficient olefins to give γ‐fluoro‐γ‐nitro‐esters, nitriles and ketones which bear a fluorinated quaternary carbon center were reported. The reactions were promoted by TMG, affording the desired adducts in acceptable to good yields.     

Modification of Nano-alumina Surface by Michael Addition Reaction

With recent interest in polymer-based nanocomposites, nano-alumina has receivedconsiderable attention because of their high hardness, high strength and good wearresistance. Improvements in mechanical, tribological, conductive and barrier propertiesof some…     

环己酮与查尔酮的无溶剂Michael加成反应

以环己酮和查尔酮为原料, 在 NaOH 存在下无溶剂室温研磨反应, 非常方便地得到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, ¹H NMR和元素分析确证产物的结构.     

基于迈克尔加成反应的沙门氏菌纳米荧光标记研究

本文通过迈克尔加成反应的荧光标记法,成功构建了纳米荧光探针标记的沙门氏菌(YB1-INPs)。采用三(2-羧乙基)膦将沙门氏菌YB1外膜蛋白表面上的二硫键温和还原为巯基后,与吲哚菁绿(ICG)@纳米探针(INPs)的马来酰亚胺基团(Mal)交联形成YB1-INPs。通过扫描电镜和共聚焦荧光成像对YB1-INPs的形貌、光学性质进行表征。通过活死细菌染色和LB琼脂平板实验对YB1-INPs的活性进行考察。结果表明,INPs成功标记到沙门氏菌YB1表面后对YB1的形态、光学性质、活性及生长均没有产生影响,并且能够用于沙门氏菌YB1体内靶向的荧光分布成像。本研究提供的这种简单、安全、高效的荧光标记方法能够将纳米材料标记到生物载体上,可以应用于生物载体的药物输送和体内监测。     

硫脲衍生物有机催化蒽酮与硝基烯烃的不对称Michael加成反应

将硫脲衍生物用于有机催化蒽酮和β-硝基烯烃的不对称Michael加成反应.考察溶剂、温度及催化剂用量等对反应催化性能的影响.结果表明,最佳催化条件为5%(摩尔百分数)催化剂1f,二氯甲烷为溶剂,室温反应.得到了80%~97%的化学产率和最高达99%ee的对映选择性.     

Unprecedented Double aza‐Michael Addition within a Sapphyrin Core

A novel sapphyrin derivative was obtained from the reaction between a free‐base sapphyrin and dimethyl acetylenedicarboxylate (DMAD). The formation of the new compound involved a double aza‐Michael addition of two pyrrolic NH groups to a DMAD molecule, with the formation of a disubstituted ethano bridge. The NMR spectral data reveal a product with an unsymmetrical structure; DFT calculations provided support for a structure in which the ethano bridge links two adjacent pyrrole units. The present study provides a seemingly unprecedented example of an N,N′‐dinucleophile reacting with DMAD to form a heterocyclic compound in which the two N‐atoms are linked to the two sp³ carbon atoms derived from a substituted acetylene.     

Reaction of Iodolevoglucosenone with Ethyl Cyanoacetate under Michael Reaction Conditions

The reaction of iodolevoglucosenone with the anion of ethyl cyanoacetate via succession of tandem intramolecular reactions leads to formation of tricyclic cyclopropanolevoglucosenone or tetracyclic imine.     

Tetramethylguanidium Lactate Ionic Liquid： Catalyst-free Medium for Michael Addition Reaction

A catalyst-free, facile and efficient Michael addition reaction of active methylene compounds as well as nitromethane with chalcones catalyzed by guanidinium lactate ionic liquid was done. A series of chalcones, nitromethane, and active methylene compounds were converted smoothly to the corresponding products in high yields. The simple procedure, very mild conditions, high yields, and reuse of the IL without any loss of catalytic activity make this protocol considerably attractive for academic researches and practical applications.     

Vicarious Michael Addition

C-H bond can undergo vicarious Michael addition reaction (VMA) with double-activated double bond in the absence of strong base and catalyst under mild conditions. Intramolecular H-bonding, electron-withdrawing inductive effect, and steric hindrance at α-position of nucleophile facilitates C-H addition over N-H addition. By using VMA, high branching multiplicity, novel branching pattern, controllable density and distribution of functional groups can be envisioned for novel dendrimer synthesis.     

无溶剂条件下研磨促进的Michael加成反应——推荐一个新的半微量有机化学实验

采用研磨促进环己酮与查尔酮Michael加成反应的手段新颖,实验时间短,产率高,使用的反应容器简单,操作方便易实现,试剂用量少,是一个半微量有机实验,便于实现实验的系列化,节约实验开支。     

Michael Addition Reaction of Vinyl Sulfoxide with Poly(Vinyl Alcohol)

The Michael addition reaction of a series of alkyl vinyl sulfoxides (CH₂[dbnd]CH-SO-R; R = CH₃ (MVSO), C₂H₅ (EVSO), t-C₄H₉ (BVSO)) with poly(vinyl alcohol) (PVA) was carried out after investigating the model reaction with isopropyl alcohol. The addition reaction was found to proceed in the presence of sodium hydroxide as catalyst. This sulfinylation of PVA proceeded more easily with MVSO and EVSO than with BVSO, and a polymer containing up to 60 mol% sulfoxide unit was obtained with MVSO and EVSO. The solution viscosity as well as the solubility behavior of the modified PVA' having various types and contents of sulfoxide group were also examined.     

含分子内氢键的苯硫酚在水相中的Michael加成反应

苯硫酚的巯基是一个较强的亲核基团,对α,β-不饱和双键的Michael加成反应已有报道．但是当巯基的邻位存在与其形成氢键的基团时,如果按文献条件进行反应,或者反应无法进行,或者要使用反应条件苛刻的丁基锂,或者使用吡啶等毒性较大的反应溶剂,而且产率较低．本文选择     

Easy Michael Addition by Solid-Liquid Phase Transfer Catalysis Abnormal Reaction of N-Acetylaminomalonate

Solid-liquid phase transfer catalysis (PTC) without added solvent efficiently promotes Michael addition of substituted malonates on hindered acceptors. A rearrangement of adducts formed by addition of diethyl N-acetylaminomalonate is described.     

Synthesis of Novel Thiazoline Catalysts and Their Application in Michael Addition Reaction

Several novel chiral thiazoline catalysts containing thiazoline, thiourea and proline were efficiently synthesized from commercially available L-cysteine. These ligands were subsequently applied to the asymmetric Michael reaction between cyclohexanone and various β-nitrostyrene. The result shows that the optimal catalyst for this reaction is ligand 18d, the organocatalyst with thiazoline, thiourea and chiral proline motif, which efficiently promotes the enantioselective conjugate addition of cyclohexanone to various nitroalkenes to yield the corresponding addition products in high to excellent yields with enantiomeric excess(e.e.) up to 95% and diastereoselectivity ratio(dr.) up to 99:1.     

阴离子交换树脂催化丙烯腈与二醇的Michael加成反应

利用阴离子交换树脂为催化剂进行了丙烯腈与二醇的Ｍｉｃｈａｅｌ加成反应的研究，对影响反应的诸因素进行了讨论，产物收率为７０－９０％。     

Highly Efficient Michael Addition Reaction of Amines Catalyzed by Silica-Supported Aluminum Chloride

Aliphatic and aromatic amines undergo smooth nucleophilic addition to α,β-unsaturated compounds in the presence of a catalytic amount of silica-supported aluminum chloride at 60 °C and under solvent-free conditions to produce the corresponding β-amino compounds in excellent yields. This method is simple and convenient and works efficiently under mild conditions. This catalyst can used again without losing its activity three times.     

Syntheses of Polycyclic Natural Products Employing the Intramolecular Double Michael Reaction

The one-pot intramolecular double Michael reaction of compounds having two different α, β-unsaturated carbonyl groups to form polycyclic compounds can be carried out by three different methods: in the first the substrate is treated with lithium hexamethyldisilazide, in the second with chlorotrimethylsilane, triethylamine, and zinc chloride at an elevated temperature, and in the third with tert-butyldimethylsilyl trifluoromethanesulfonate and triethylamine. The reaction proceeds with complete regioselectivity and high stereoselectivity following a stepwise mechanism. Spiro-fused bicyclo[2.2.2]octane derivatives can be constructed with high stereoselectivity by the intromolecular double Michael reaction by using the first method. Enantiomerically pure atisine and the enantiomer of atisirene were synthesized stereoselectively by application of this methodology. The syntheses of steroids and angular triquinane-type sesquiterpenoids were possible with the second method. Heterocyclic compounds with a bridgehead nitrogen atom were obtained by the reaction of α, β-unsaturated amides following the second and third methods. The asymmetric synthesis of tylophorine with diastereofacial control was achieved by the intramolecular reaction according to the third method. The sulfur-mediated intramolecular double Michael reaction utilizing the third method produced trans-hydroindane derivatives. Furthermore, the intramolecular Michael-aldol reaction can be employed in synthesizing polycyclic systems with cyclobutane units by treatment with tert-butyldimethylsilyl trifluoromethanesulfonate in the presence of triethylamine. The intermolecular double Michael reaction and related reactions will also be described.