伯醇的脱羟甲基反应的研究进展

伯醇来源广泛且廉价易得,是生产各种化学品,如农用化学品、食品添加剂、香料和药物等的重要化工原料.伯醇的脱羟甲基反应是一种利用伯醇制备少一个碳原子的碳氢化合物的方法,在生物质降解和药物合成等方面有着广泛的应用,引起了有机化学家的关注.根据反应类型综述了伯醇的脱羟甲基反应的发展,根据反应特点分为四个部分综述:过渡金属催化脱羟甲基转化为甲烷和水的反应、过渡金属催化脱羟甲基转化为一氧化碳和氢气的反应、过渡金属催化脱羟甲基转化为甲醛的反应、无过渡金属脱羟甲基转化为甲酸和水的反应.主要从反应体系、适用范围、反应机理等方面阐述了伯醇的脱羟甲基反应的研究进展.     

过渡金属催化的炔烃芳构化反应

综述了过渡金属催化的炔烃环三聚芳构化反应的历史沿革及最新研究进展，并 重点对含有不同电性取代基的炔烃环三聚反应、几种典型的催化体系和作用机理、 该领域的一些前沿热点作了评述．     

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.     

钴催化异腈参与的偶联反应研究进展

异腈是一种含有稳定二价碳原子的重要活性反应物,在含氮化合物的构建、新药物的研发以及天然产物的合成中得到了广泛的应用.在过去的十年中,以Passerini和Ugi反应为基础,化学家们致力于研究异腈参与的多组分反应.最近,过渡金属催化异腈参与的氧化偶联反应得到广泛的发展,而使用的催化剂主要集中在一些贵重的过渡金属（Pd、Rh、Ag等）化合物,如何利用廉价过渡金属Co来催化异腈参与的偶联反应具有非常重要的意义.在这里我们概述了近年来Co催化异腈参与的偶联反应的最新研究进展.     

无过渡金属参与的羰基化反应进展

一氧化碳是来源广泛和廉价的碳一资源.直接将其作为羰基源引入有机分子中的羰基化反应是化学化工研究的前沿领域之一.近年来,无过渡金属参与的羰基化反应引起了人们的高度关注.综述了无过渡金属参与的羰基化合成醛与酮、合成酯、合成酰胺、合成酸和酸酐以及合成酰氯和醇等重要羰基化反应的研究现状,并对无过渡金属参与的羰基化反应的发展及应用前景进行了展望.     

甲醇芳构化反应中Ag/ZSM-5催化剂的失活特性

通过四次连续反应-再生循环实验对甲醇芳构化催化剂Ag/ZSM-5进行了失活再生研究,结果表明催化剂通过烧碳可以得到部分再生.对反应-再生后的催化剂进行了X射线衍射(XRD)、透射电子显微镜(TEM)表征,证实芳构化过程中催化剂的ZSM-5骨架结构保持完好,金属烧结也不严重.傅里叶红外光谱(FTIR)和氨-程序升温脱附(NH3-TPD)实验证实了反应生成的水使催化剂在475℃发生水热脱铝,进而导致Brφnsted酸流失及催化剂的芳构化反应能力不可逆下降.     

金属钯催化的吡咯分子间不对称烯丙基去芳构化反应

正手性2H-吡咯类化合物是有机合成中一类重要的合成中间体.通过催化不对称去芳构化反应,可以实现直接由吡咯类化合物来构建这类骨架.然而,目前文献上报道的对取代吡咯类化合物的直接催化去芳构化反应主要集中在过渡金属催化的不对称[4+3]环加成反应和氢化反应.由于反应过程中可能面临的化学选择性、区域选择性和对映选择性等挑战性问题,通过烷基化反应来实现吡咯环的分子间不对称去芳构化反应迄今还没有被报道.中国科学院上海有机化学研究所游书力课题组成功地通过使用烯丙基取代反应实现了取代吡咯的分子间催化不对称去芳构化.使用取代的吡咯化合物1和烯丙基碳酸酯2在金属钯和商业可得的手性配体(R)-segphos的作用下,可以以高达     

添加Ru的Mo/HZSM-5催化体系上的甲烷无氧脱氢芳构化

研究了在Ｍｏ／ＨＺＳＭ－５催化剂中添加过渡金属阳离子以改变催化剂的反应性能，提高甲烷无氧脱氢芳构化的反应活性和稳定性，在添加第二组分的催化剂中，Ｍｏ－Ｒｕ／ＨＺＳＭ－５具有最佳的反应活性和稳定性，Ｒｕ的加使甲烷的转化率上原来的６％－７％提高以９．８％，采用比表面积及孔分布测定，Ｘ射线衍射，程序升温还原，程序升温氨脱附和差热分析等表征方法研究了Ｍｏ－Ｒｕ／ＨＺＳＭ－５催化剂的物理化学性质，结果表明，     

有机羰基化合物在过渡金属络合物上脱羰基反应

脱羰基反应是有机分子通过脱掉一个羰基实现减少一个碳单元的过程。近年来,在过渡金属络合物上进行化学计量或催化的脱羰基反应屡见报道,现已成为有机合成中重要的反应之一。有机化合物在过渡金属络合物的作用下     

无过渡金属参与下光诱导的偶联反应构建碳-杂键的研究进展

近年来在光照条件下无过渡金属参与的偶联反应受到了广泛的关注,这些反应为C-N/S/P等键的构建提供了重要的方法,也在医药、农业或材料化工等领域得到了广泛的应用.重点介绍了近五年来在无过渡金属参与下由有机光氧化还原催化剂或光敏剂诱导构建C-N/S/P等键的光氧化还原反应.     

Application of Metal-Free Dearomatization Reaction as a Sustainable Strategy to Direct Access Complex Cyclic Compounds

The highly efficient construction of complicated heterocyclic frameworks in an atom- and step-economic manner is still one of the cores of synthetic chemistry. Dearomatization reactions show the unique advantage for the construction of functionalized heterocycles and have attracted widespread attention over the past two decades. The metal-free approach has proved to be a green and sustainable paradigm for the synthesis of spirocyclic, polycyclic and heterocyclic scaffolds, which are widely present in natural products and bioactive molecules. In this review, the advances in the recent six years (2017–2023) in metal-free dearomatization reactions are highlighted. Emphasis is placed on developments in the field of organo-catalyzed dearomatization reactions, oxidative dearomatization reactions, Brønsted acid- or base-promoted dearomatization reactions, photoredox-catalyzed dearomatization reactions, and electrochemical oxidation dearomatization reactions.     

Transition Metal‐Participated Synthesis and Utilization of N‐containing Heterocycles: Exploring for Nitrogen Sources

This account aims to describe our recent efforts on the synthesis and utilization of N‐containing heterocycles, where transition metals participate in the synthesis. A variety of nitrogen sources, including amines, amides, hydrazones, pyrimidines, isocyanides, and copper nitrate, have been disclosed for the synthesis of diverse bioactive and pharmacologically interesting N‐containing heterocycles under the participation of transition metals. The well‐known nitrogen sources, such as amines and amides, were used for the construction of indoles, isatins, and quinolones. Dihydrophthalazines, isoquinolines, indazoles, and pyrazoles were obtained from hydrazones, while various pyrimidine‐containing heterocycles were afforded through regioselective C?H functionalizations using pyrimidine as the directing group. Recent research has focused on the chemistry of isocyanides to achieve several kinds of heterocyclic compounds with high efficiency under the catalysis of transition metals (Pd, Rh, Mn, Cu), through oxidative cyanation reactions, sequential isocyanide insertions into C?H, N?H, or O?H bonds, and tandem radical annulation. More recently, an efficient route to isoxazolines has been reported using copper nitrate as a novel nitrogen source.     

苯炔参与的去芳构化反应研究进展

去芳构化反应是有机化学热点研究领域之一,可从二维平面分子出发构筑高官能团化的三维立体分子.近年来,苯炔作为一类高活性中间体被有机化学家们广泛用于去芳构化反应研究中,并取得了一系列创新成果.从含氮芳杂环同苯炔的去芳构化反应、苯炔与双烯体的[4+2]环加成去芳构化反应以及苯炔以其它途径参与的去芳构化反应三个方面,对机理进行系统性综述,并对该类反应未来的发展方向予以展望.     

2-碘酰基苯甲酸在有机合成中的研究与应用

高价有机碘化合物的反应性质与过渡金属相似,其参与的反应具有反应条件较温和、选择性好、产率高及环境友好等优点,因而近年来关于高价有机碘试剂的研究受到广泛关注,在有机合成领域中获得了较多应用.综述了近年来高价有机碘试剂2-碘酰基苯基酸(IBX)在有机合成中的研究及应用,包括IBX在氧化羟基、含氮化合物和含硫化合物,在制备αβ-不饱和羰基化合物和α,β-不饱和酯,以及在不对称合成等方面的应用.最后介绍了近期对IBX的改进.     

Catalytic Asymmetric Dearomatization Reactions

This Review summarizes the development of catalytic asymmetric dearomatization (CADA) reactions. The CADA reactions discussed herein include oxidative dearomatization reactions, dearomatization by Diels–Alder and related reactions, the alkylative dearomatization of electron‐rich arenes, transition‐metal‐catalyzed dearomatization reactions, cascade sequences involving asymmetric dearomatization as the key step, and nucleophilic dearomatization reactions of pyridinium derivatives. Asymmetric dearomatization reactions with chiral auxiliaries and catalytic asymmetric reactions of dearomatized substrates are also briefly introduced. This Review intends to provide a concept for catalytic asymmetric dearomatization.     

Niobium‐bearing arsenides and germanides from elemental mixtures not involving niobium: a new twist to an old problem in solid‐state synthesis

Three isostructural transition‐metal arsenides and germanides, namely niobium nickel arsenide, Nb_0.92(1)NiAs, niobium cobalt arsenide, NbCoAs, and niobium nickel germanide, NbNiGe, were obtained as inadvertent side products of high‐temperature reactions in sealed niobium containers. In addition to reporting for the very first time the structures of the title compounds, refined from single‐crystal X‐ray diffraction data, this article also serves as a reminder that niobium containers may not be suitable for the synthesis of ternary arsenides and germanides by traditional high‐temperature reactions. Synthetic work involving alkali or alkaline‐earth metals, transition or early post‐transition metals, and elements from groups 14 or 15 under such conditions may yield Nb‐containing products, which at times could be the major products of such reactions.     

Transition‐Metal‐Catalyzed CS Bond Coupling Reaction

Sulfur‐containing molecules such as thioethers are commonly found in chemical biology, organic synthesis, and materials chemistry. While many reliable methods have been developed for preparing these compounds, harsh reaction conditions are usually required in the traditional methods. The transition metals have been applied in this field, and the palladium‐catalyzed coupling of thiols with aryl halides and pseudo halides is one of the most important methods in the synthesis of thioethers. Other metals have also been used for the same purpose. Here, we summarize recent efforts in metal‐catalyzed C? S bond cross‐coupling reactions, focusing especially on the coupling of thiols with aryl‐ and vinyl halides based on different metals.     

Synthesis of symmetrical biaryl compounds by homocoupling reaction

Since the development of the Ullmann coupling in the early 20th Century, there has been intense and continuous research on the syntheses of biaryl compounds, which appears as an interesting branch of organic chemistry.A myriad of methodologies for the synthesis of biaryl compounds have been studied and well established, including homocoupling methodologies, which in general are robust as well as consolidated strategies. Biaryl systems are quite relevant building blocks for the synthesis of more complex chemical structures. Besides the diversity of functional groups that can be used to promote a new aryl-aryl bond, there is a wide variety of transition metals that can act as catalyst in these processes.In this review, we summarized numerous methodologies of homocoupling reactions for the synthesis of symmetrical biaryl compounds.     

Synthesis of (±)‐Tetrapetalone A‐Me Aglycon

The first synthesis of (±)‐tetrapetalone A‐Me aglycon is described. Key bond‐forming reactions include Nazarov cyclization, a ring‐closing metathesis promoted with complete diastereoselectivity by a chiral molybdenum‐based complex, tandem conjugate reduction/intramolecular aldol cyclization, and oxidative dearomatization.     

3 d Transition Metal‐Catalyzed Hydrogenation of Nitriles and Alkynes

Selective hydrogenation of nitriles and alkynes is crucial considering the vast applications of reduced products in industries and in the synthesis of bioactive compounds. Particularly, the late 3d transition metal catalysts (manganese, iron, cobalt, nickel and copper) have shown promising activity for the hydrogenation of nitriles to primary amines, secondary amines and imines. Similarly, semihydrogenation of alkynes to E‐ and Z‐alkenes by 3d metals is adequately successful both via the transfer hydrogenation and by using molecular hydrogen. The emergence of 3d transition metals in the selective synthesis of industrially relevant amines, imines and alkenes makes this protocol more attractive. Herein, we provide a concise overview on the late 3d transition metal‐catalyzed hydrogenation of nitriles to amines and imines as well as semihydrogenation of alkynes to alkenes.