联苯类化合物的合成

联苯类化合物是一类极为重要的有机合成中间体,在有机合成中往往通过有机金属偶联反应构建此类化合物.以反应底物分类综述了近年来通过偶联反应合成此类化合物的方法,详细介绍了以卤代芳烃与芳基金属化合物为底物的反应.     

Oxa-Michael加成反应的研究新进展

Oxa-Michael加成反应是一类重要的反应, 经常被用于天然产物的合成, 但该反应直到近几年才被深入研究. 简要综述了oxa-Michael加成反应的研究进展.     

Tandem Hass-Bender/Henry reaction for the synthesis of dimethylnitro alcohols from benzylic halides

Dimethylnitro alcohols are constructed in a one-pot process from benzylic halides and 2-nitropropane. The use of tetrabutylammonium fluoride (TBAF) as the promoter is essential for this tandem Hass-Bender/Henry reaction to proceed.     

Extension of solution‐reaction‐surface description to examination of nonequilibrium solvation effect for microsolvated reaction

A microscopic method to examine a nonequilibrium solvation effect is reported. The solution reaction is simplified as a barrier‐crossing reaction within a solution reaction surface that corresponds to a two‐dimensional space determined by solute and solvent reactive coordinates. For this simplification, the motions within the space spanned by nonreactive coordinates are frozen. We derive three rate constant expressions: (1) in the nonadiabatic solvation limit, (2) in the equilibrium solvation limit, and (3) of the transition‐state theory. This method was applied to the examination of the contact‐ion‐pair formation of t‐BuCl in four waters. We found that the nonadiabatic solvation picture overestimates the nonequilibrium solvation effect. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 77: 791–796, 2000     

Recent advances in ionic liquids: green unconventional solvents of this century: part I

Abstract

The present overview describes ionic liquids as alternate, attractive solvents of today and tomorrow in organic synthesis. Since this subject is too wide and developments have been too fast, only a recent account is presented on indispensable carbon-carbon bond forming named reactions such as Knoevenagel, Michael Aldol, Biginelli Reaction, and so on, which has never been done before exclusively.     

Functionalization of dihydrodipyridopyrazines involving palladium-catalyzed coupling reactions

Various 4-substituted dihydrodipyridopyrazines were synthesized by palladium-mediated cross-coupling reactions. Starting from the corresponding 4-iodo or 4-bromo derivatives, the incorporation of aryl, vinyl, alkynyl and methoxycarbonyl groups is described.     

Oxidative addition of N-halosuccinimides to palladium(0): the discovery of neutral palladium(II) imidate complexes, which enhance Stille coupling of allylic and benzylic halides

The Stille coupling of organostannanes and organohalides, mediated by air and moisture stable palladium(II) phosphine complexes containing succinimide or phthalimide (imidate) ligands, has been investigated. An efficient synthetic route to several palladium(II) complexes containing succinimide and phthalimide ligands, has been developed. cis-Bromobis(triphenylphosphine)(N-succinimide)palladium(II) [(Ph₃P)₂Pd(N-Succ)Br] is shown to mediate the Stille coupling of allylic and benzylic halides with alkenyl, aryl and allyl stannanes. In competition experiments between 4-nitrobromobenzene and benzyl bromide with a cis-stannylvinyl ester, (Ph₃P)₂Pd(N-Succ)Br preferentially cross-couples benzyl bromide, whereas with other commonly employed precatalysts 4-nitrobromobenzene undergoes preferential cross-coupling. Furthermore, preferential reaction of deactivated benzyl bromides over activated benzyl bromides is observed for the first time. The type of halide and presence of a succinimide ligand are essential for effective Stille coupling. The type of phosphine ligand is also shown to alter the catalytic activity of palladium(II) succinimide complexes.     

N-硬脂酰基亮氨酸的合成

采用酰氯化反应与缩合反应两步法合成N -硬脂酰基亮氨酸。以硬脂酸和亚硫酰氯为原料 ,n(硬脂酸 )∶n(亚硫酰氯 ) =1∶1 .5 ,在 80℃下冷凝回流 6h酰氯化反应合成硬脂酰氯 ,硬脂酰氯经减压蒸馏收集 1 70～2 0 0℃的馏分得到。硬脂酰氯收率为 65 %。硬脂酰氯再与亮氨酸的氢氧化钠溶液在冰水浴中进行Schotten -Baumann缩合反应制得N -硬脂酰基亮氨酸。缩合反应最佳工艺条件是反应溶液pH值控制为 9.0。反应后滴加1mol/L盐酸至pH =5 .0～ 6.0 ,加入正己烷使N -硬脂酰基亮氨酸处于水层中 ,分离并蒸干水层溶液得含NaCl的混合物。用无水乙醇萃取混合物 ,萃取液蒸干得产物。N -硬脂酰基亮氨酸收率为 75 %     

Towards click chemistry: Multicomponent reactions via combinations of name reactions

In this report, we try to show the importance of incorporation of name reactions in the sequential cascade reaction in which significantly decreasing the number of steps towards an ideal and practical multi-step synthesis of natural products as well showing virtually all the advantages already mentioned for “Click Chemistry”. In addition, since the chiral inductions are desired for most of these sequential name reactions, their asymmetric catalyzed reactions were also described.     

Machine learning modelling of chemical reaction characteristics: yesterday,today, tomorrow

The synthesis of the desired chemical compound is the main task of synthetic organic chemistry. The predictions of reaction conditions and some important quantitative characteristics of chemical reactions as yield and reaction rate can substantially help in the development of optimal synthetic routes and assessment of synthesis cost. Theoretical assessment of these parameters can be performed with the help of modern machine-learning approaches, which use available experimental data to develop predictive models called quantitative or qualitative structure–reactivity relationship (QSRR) modelling. In the article, we review the state-of-the-art in the QSRR area and give our opinion on emerging trends in this field.     

Cl+C2H6→HCl+C2H5反应的准经典轨线研究

用三原子模型的准经典轨线方法研究了Ｃｌ与Ｃ２Ｈ６（ｖ＝０，ｊ）的反应。计算结果表明，反应产物ＨＣｌ的角度分布基本上为各向同性，其振动分布处于基态，与实验结果相一致。对反应轨线的研究表明，该反应为一直接反应，而且反应碰撞在低及高的碰撞参数下的机理不一样，在低碰撞参数下反应碰撞是直接完成的，产物ＨＣｌ以向后散射为主，转动基本上是冷的，但比高碰撞参数下的热。在高的碰撞参数下则生成短寿命的碰撞复合物，产物     

Biginelli reaction for synthesis of novel trifluoromethyl derivatives of bis(tetrahydropyrimidinone)benzenes

A facile one-pot three-component condensation of terephthalic aldehyde with urea and fluorinated 1,3-dicarbonyl derivatives is developed using catalytic quantities of chlorotrimethylsilane at ambient temperature. As a consequence, efficient synthesis of novel trifluoromethyl derivatives of bis(tetrahydropyrimidinone)benzenes is observed within short time periods. The procedure is shown to be equally efficient when urea is replaced with thiourea or guanidine.     

A microwave-assisted, copper-catalyzed three-component synthesis of dihydropyrimidinones under mild conditions

The synthesis of dihydropyrimidinones via a clean multi-component Biginelli reaction under microwave irradiation is reported. The copper-catalyzed process proved to be simple, efficient, economical, and environmentally friendly.     

生物质平台化合物电催化制备高值燃料与化学品研究进展

生物质是一类丰富的可再生碳基资源,有望代替传统化石资源生产燃料和化学品,受到了广泛关注和研究.近年来,电催化作为一种绿色高效的转化策略,成为生物质催化转化的重要研究方向之一,具有巨大的应用前景.本文总结了生物质平台化合物电催化制备高附加值燃料与化学品的研究进展,根据反应类型重点介绍了电催化氧化、还原和偶联反应,对催化反应过程和机理进行了阐述,并对电催化生物炼制的前景进行了展望.     

Recent Advances of Single-atom Catalysts for Electro-catalysis

Single-atom catalysis is the “hot spot” in the field of catalysis due to the special geometries, electronic states, and their unique catalytic performance. Single-atom catalysts(SACs), isolated metal atoms dispersed on the support, show the highest atom efficiency, cutting down the potential cost in the industrial process. Consequently, this “homo-hetero” catalyst could be a promising candidate for the next-generation catalysts. The applications for the SACs are widely reported, like gas-solid reactions, organic reactions, and electro-catalysis. In this mini- review, we will focus on the recent work of SACs on electro-catalysis, including hydrogen evolution reaction(HER), oxygen reduction reaction(ORR), oxygen evolution reaction(OER), CO₂ reduction reaction(CO₂ RR), and nitrogen reduction reaction(NRR).     

Recent advances in ionic liquids: green unconventional solvents of this century: part II

Abstract

In the second part of our paper, further recent developments of ionic liquids in selected name reactions of carbonyl chemistry such as Mannich, Reformatsky, Cannizaro, Streacker, Barbier, Pechmann, etc. are described.     

Palladium bis(2,2,6,6-tetramethyl-3,5-heptanedionate) catalyzed Suzuki, Heck, Sonogashira, and cyanation reactions

Palladium bis(2,2,6,6-tetramethyl-3,5-heptanedionate): a structurally well-defined O-containing transition metal complex is reported as an efficient catalyst for Suzuki, Heck, and Sonogashira cross-coupling reactions. The protocol was also applied successfully for cyanation of aryl halides under milder operating conditions. The system tolerated the coupling of various aryl halides with alkenes, alkynes, and organoboronic acid along with the cyanation of aryl halides providing good to excellent yields of desired products.     

3-Benzoylquinoxalin-2(1H)-one in the Kostanecki-Robinson Reaction. Synthesis and Structure of 2-Oxo-4-phenylpyrano[2,3-b]quinoxaline

3-Benzoylquinoxalin-2(1H)-one is cyclized with acetic anhydride in the presence of pyridine into 2-oxo-4-phenylpyrano[2,3-b]quinoxaline.     

Synthesis of the 6′-iso analogues of neplanocin A and 5′-homoneplanocin A

An efficient synthesis of 6′-isoneplanocin A and 6′ -isohomoneplanocin A is reported. The key steps in the synthesis include an enyne metathesis and a regioselective oxidation.     

Convergent multicomponent assembly of 2-acyloxymethyl thiazoles

Diverse substituted 2-acyloxymethyl thiazoles can be assembled by a new multicomponent reaction (MCR) of methyl 3-(N,N-dimethylamino)-2-isocyanoacrylate, aldehydes and thiocarboxylic acid under Lewis acid catalysis. The reaction is performed under mild conditions and is compatible with a wide range of functionalized starting materials. 13 examples are given.