Cu(Ⅰ)有机化合物在有机合成中的应用

一、前言过渡金属有机化合物在近代有机合成中,日益显示出其重要作用,为有机合成工作提供了许多崭新而独特的新方法。 Cu(Ⅰ)有机化合物近十多年来在有机合成中的应用,正可以作为这方面有力的例证。 Cu(Ⅰ)有机化合物中含有碳负离子,属于亲核进攻试剂,在某些取代反应中,Cu(Ⅰ)有机化合物比传统的格林纳试剂(RMgX)及有机锂化     

无过渡金属参与下Selectfluor作为“无氟”官能化试剂在有机合成中的应用

Selectfluor是一种性能优越的商品化的亲电氟化试剂,广泛应用于氟化反应中.近年来Selectfluor作为"无氟"官能化试剂在有机合成中得到较广泛的应用,尤其是利用Selectfluor与过渡金属的协同催化体系催化反应,取得了较大的进展.然而,该催化体系存在过渡金属价格昂贵、污染环境等问题.因此, Selectfluor作为"无氟"官能化试剂在无过渡金属参与下的应用受到越来越多的关注.根据反应类型综述了无过渡金属参与下Selectfluor作为"无氟"官能化试剂在有机合成中的应用,并对其前景进行了展望.     

三乙胺三(氟化氢)在有机合成中的应用

氟化反应在有机合成中有着广泛的应用, 三乙胺三(氟化氢)作为氟化试剂有着其它氟化试剂所无法比拟的优越性. 对近年来三乙胺三(氟化氢)在有机合成中的应用进行了总结和概述, 重点介绍了亲核取代、环氧开环反应、亲电加成反应和脱硅保护基等反应.     

烯丙型膦叶立德与卟啉铁卡宾反应: 催化的高效、高选择性的分子间卡宾对烯烃C—H键形式插入反应

叶立德作为带有特殊离去基团的碳负离子(亲核试剂)被广泛应用于有机合成研究. 传统的叶立德参与的反应主要有叶立德同亲电的羰基化合物、亚胺以及烯烃的反应, 分别生成烯烃和环氧化合物、氮杂环丙烷化合物以及环丙烷化合物. 亲电的金属卡宾作为一类重要的亲电试剂, 其同叶立德的反应研究报道则很少. 最近, 中国科学院上海有机化学研究所唐勇等发现, 酯基稳定的卟啉铁卡宾可以高效、高选择性地插入到烯丙型膦叶立德的C—H键中. 机理研究表明, 反应经历环丙烷化-开环重排反应的串联过程. 在此基础上, 高立体选择性地实现了1,1,4-三取代共轭丁二烯衍生物的合成, 反应具有很好普适性. 该发现提供了叶立德与金属卡宾(亲电试剂)反应的一种新模式.     

钛、锆有机化合物在有机合成中的应用

许多钛、锆有机化合物可作为亲核金属有机试剂。它们有较高的化学选择性和立体化学选择性,在有机合成中的应用日益广泛。一、亚烷基化 Wittig试剂能将酮醛亚烷基化,但它具有强碱性,能使酮醛消旋化和烯醇化。在同一体     

有机磺酰氯参与的磺酰化及脱磺酰化反应

作为一类活泼的亲电试剂,有机磺酰氯参与的脱磺酰化偶联反应已经发展成为一个新的研究热点.在适当的温度以及钯等过渡金属络合物的催化下,磺酰氯可以和多种亲核试剂发生脱磺酰化偶联反应,并在一些重要有机合成反应中显示出良好的应用前景.有鉴于此,特就过渡金属催化下磺酰氯的脱磺酰化交叉偶联的研究进展进行简要的评述,并与相应的磺酰化反应进行对照,以其找出脱磺酰化偶联的关键因素,为以后的相关研究提供参考.     

镍催化构筑C(sp3)—C(sp3)键反应研究进展

过渡金属催化的偶联反应是构筑C-C键的高效方法,在有机合成中得到了广泛的应用.然而,相对于Heck反应、Negishi偶联与Suzuki偶联等构筑C（sp²）-C（sp²）键的反应,过渡金属催化的构筑C（sp³）-C（sp³）键的偶联反应较难进行,发展较晚.近年来,烷基-烷基C-C键偶联反应受到广泛的重视,一些高效催化剂被开发出来,其中镍催化剂展示出独特的催化活性和选择性.本文将综述镍催化烷基-烷基C-C键偶联反应最新研究进展,主要包括烷基亲电试剂与金属有机试剂交叉偶联反应、导向基参与的C（sp³）-H键活化的偶联反应、镍-光反应催化剂协同催化偶联反应、烷基亲电试剂与亲电试剂的还原偶联反应和镍催化烯烃加成反应等.     

电化学固定CO2构建羧酸衍生物的研究进展(英文)

CO₂由于其含量丰富、无毒和低成本等特性可作为有机合成中的重要C1源,因此,使用CO₂作为C1源合成高附加值的化合物具有重要的意义.本综述重点介绍了在电化学条件下使用CO₂作为亲电试剂参与有机化合物羧化反应的最新进展.主要介绍了非活化有机卤化物、不饱和烯烃化合物和一些特殊化合物的电化学羧化,并就使用和不使用牺牲阳极进行了详细分类,讨论了这些反应的反应机制,为今后此类反应在有机合成中的应用提供参考.     

锆-苯炔参与的金属杂环的形成及其在有机合成中的应用

锆-苯炔是一类非常重要且具有高度反应活性的金属有机配合物.其与烯、炔、醛、酮、腈等不饱和底物反应时,通过调节底物的取代基、化学计量比、配体结构以及反应条件等,可以得到多种形式的锆杂环类化合物.该锆杂环进一步与亲电试剂反应可以构筑结构丰富多样的有机化合物.对锆-苯炔的合成方法及其参与的金属杂环的形成与后续反应等方面进行了综述,并对锆-苯炔在有机合成化学领域的发展前景进行了展望.     

镍催化的三级卤代烷烃与烯丙基碳酸酯的还原偶联反应

正Angew.Chem.Int.Ed.2017,56,13103~13106烷基类化合物的烯丙基化反应是现代有机合成化学中一类重要的反应类型,有着广泛的应用价值.同时,季碳化合物的合成在有机化学中极具挑战性,在材料化学和药物分子领域等也有良好的应用前景.目前主要是通过传统偶联方法,在过渡金属Co、Ni、Cu以及Pd等催化下卤代烷烃或其与金属有机试剂与相应的亲核或亲电试剂发生偶     

Nickel and palladium <Emphasis Type="Italic">N</Emphasis>-heterocyclic carbene complexes. Synthesis and application in cross-coupling reactions

N-Heterocyclic carbenes (NHCs) are widely used as ligands in catalysis by transition metal complexes. The catalytic activity of transition metal NHC complexes is much higher than that of the transition metal complexes bearing the phosphine and nitrogen-containing ligands. They show excellent catalytic performance in different transformations of the organic compounds, especially in the carbon—carbon and carbon—element bond forming reactions. Palladium NHC complexes are very efficient catalysts for the cross-coupling reactions. On the other hand, nickel is less expensive and regarded as a promising alternative to palladium and, therefore, it attracts increasing attention from the researches. The present review is focused on the recent advances in the synthesis of N-heterocyclic carbene complexes of nickel and palladium and their application in catalysis of cross-coupling reactions of organic, organoelement and organometallic compounds with organic halides.     

Photoactive Nickel Complexes in Cross-Coupling Catalysis

Transition metal catalyzed cross-coupling reactions are important in chemical synthesis for the formation of C−C and C-heteroatom bonds. Suitable catalysts are frequently based on palladium or nickel, and lately the cheaper and more abundant first-row transition metal element has been much in focus. The combination of nickel catalysis with photoredox chemistry has opened new synthetic possibilities, and in some cases electronically excited states of nickel complexes play a key role. This is a remarkable finding, because photo-excited metal complexes are underexplored in the context of organic bond-forming reactions, and because the photophysics and the photochemistry of first-row transition metal complexes are underdeveloped in comparison with their precious metal-based congeners. Consequently, there is much potential for innovation at the interface of synthetic-organic and physical-inorganic chemistry. This Minireview highlights recent key findings in light-driven nickel catalysis and identifies essential concepts for the exploitation of photoactive nickel complexes in organic synthesis.     

Cyclometalation Reactions

Reactions of transition metal complexes in which an organic ligand undergoes intramolecular metalation with formation of a metal-carbon σ bond are termed cyclometalation reactions. This article provides a general summary of our knowledge of these reactions, and discusses them in terms of their scope, mechanisms, and utility in organic synthesis, particularly of heterocyclic molecules.     

Asymmetric transfer hydrogenation: chiral ligands and applications

Hydrogen transfer reduction processes are attracting increasing interest from synthetic chemists in view of their operational simplicity and high selectivity. In this tutorial review the most significant advances recently achieved in the stereoselective reduction of unsaturated organic compounds catalyzed by homogeneous transition metal complexes are critically reviewed. A sharp growth of the synthetic applications of this technique in the synthesis of fine chemicals is predictable as the use of transition metal catalyzed reactions will become more familiar to synthetic chemists.     

过渡金属膦配合物在硅氢化反应中的应用研究

过渡金属膦配合物在有机合成和催化反应中的应用非常广泛, 大量含膦杂原子配体被设计合成, 利用其特定的配位能力, 和过渡金属配位成过渡金属膦配合物, 并测试其对特定有机化学反应的催化性能. 硅氢加成反应是有机硅化学中的重要反应, 多种过渡金属包括铂、钯、铑、钌等的膦配合物对于硅氢加成反应均有催化活性. 综述了近几年来过渡金属膦配合物在硅氢加成反应中的应用进展.     

Nickel-mediated regioselective [2 + 2 + 2] cycloaddition of carboryne with alkynes

Transition metal-benzyne complexes have found many applications in organic synthesis, mechanistic studies, and the synthesis of functional materials. In sharp contrast, the chemistry of transition metal-carboryne complexes, especially late transition metal complexes, is virtually unknown. This communication reports a novel nickel-mediated regioselective [2 + 2 + 2] cycloaddition reaction of carboryne with alkynes via the Ni-carboryne intermediate (eta2-C2B10H10)Ni(PPh3)2. Because of the bulkiness of the carborane moiety, a high regioselectivity was achieved in the reactions involving unsymmetrical alkynes. This work furnishes a novel method for the preparation of highly substituted benzocarboranes which are difficult to obtain by other methods.     

Toward green catalytic synthesis—Transition metal-catalyzed reactions in non-conventional media

Solvents play a critical role in “greening” synthetic chemistry, and this is also true in catalytic organic synthesis. This review attempts to summarize the progress made in the past a few years on homogeneous and heterogeneous catalytic reactions in the non-conventional solvents, water, ionic liquids, supercritical carbon dioxide and fluorous carbons, with the focus on those catalyzed by transition metal complexes. The reactions covered include hydrogenation, hydroformylation, carbonylation, Heck reactions, Suzuki and Stille couplings, Sonogashira reactions, allylic substitution, olefin metathesis, olefin epoxidation and alcohol oxidation.     

Bis(oxazolinyl)phenyl transition metal complexes: synthesis, asymmetric catalysis, and coordination chemistry

Molecular catalysts for organic synthesis should be constructed to be tailored to target reactions and their desirable conditions. In our search for them, we have studied new types of transition metal molecular catalysts dressed with a tridentate N,C,N modular ligand, which consists of a C2-symmetric side-by-side phenyl group with chiral bis(oxazolinyl) substituents. The ligand, 2,6-bis(oxazolinyl)phenyl abbreviated as Phebox, can connect covalently to transition metals by the central carbon atom. Here, we review our recent work on the chemistry of Phebox and its metal complexes, including preparation, structural analysis, asymmetric Lewis acid catalysis, asymmetric hydrosilylation, asymmetric conjugate reduction, asymmetric reductive aldol reaction, and organometallic reactions.     

Palladium(O)-mediated Formation of γ-Methylene-γ-butyrolactone from allyl 4-pentenoate

Synthetic organic reaction by means of transition metal carboxylate complexes continues to be a subject of active interest,¹ in which the transition metal carboxylate complexes are generally generated by oxidative addition of allylic esters to low-valent transition metal complexes. It also relates closely to the utilization of carbon dioxide in organic synthesis by means of transition metal complexes, because carbon dioxide insertion into the transition metal-carbon bonds produces the transition metal carboxylate complexes.² Very recently we have reported the formation of γ-butyroiactone by the reaction of bis (π-allyl)nickel (II) with carbon dioxide via a π-allynickel (II) 3-butenoate complex.³ Here we report Pd(PPh₃)₄- induced     

水溶性氮杂环卡宾金属配合物的研究进展

氮杂环卡宾(NHCs)金属配合物作为一类重要的催化剂一直是有机合成领域研究的热点。近年来,通过引入水溶性配体而得到的水溶性氮杂环卡宾过渡金属配合物受到广大科研工作者的青睐。本文主要总结了水溶性NHCs的分类、合成及其在C-C偶联反应、复分解反应以及催化加氢反应中的应用,并对水溶性NHCs金属配合物的发展趋势进行了展望。