Mechanistic aspects of transition metal-catalyzed hydrogen transfer reactions

In this tutorial review recent mechanistic studies on transition metal-catalyzed hydrogen transfer reactions are discussed. A common feature of these reactions is that they involve metal hydrides, which may be monohydrides or dihydrides. An important question is whether the substrate coordinates to the metal (inner-sphere hydrogen transfer) or if there is a direct concerted transfer of hydrogen from the metal to substrate (outer-sphere hydrogen transfer). Both experimental and theoretical studies are reviewed.     

Rapid formation of triarylphosphines by microwave-assisted transition metal-catalyzed C-p cross-coupling reactions

Rapid, direct transition metal-catalyzed C-P(III) cross-coupling reactions were performed by microwave dielectric heating, employing diphenylphosphine and aryl halides/triflates as substrates. Depending on the specific aryl halide/triflate precursor, the highest yields were obtained utilizing heterogeneous or homogeneous Pd or Ni catalysts in DMF or NMP in the presence of KOAc or DABCO as a base. [reaction: see text]     

Reactivity and selectivity of 1,3-diyn-6-enes in electrophilic transition metal-catalyzed reactions

[Structure: see text] 1,3-diyne is an excellent source of alkynyl metal carbene species upon activation with an electrophilic metal catalyst. The products from this bond reorganization process suggest that the metal carbene species, generated from the preferential participation of an acetate over an alkene in the first step, undergo an efficient metallotropic [1,3]-shift followed by termination via cyclopropanation.     

过渡金属催化高选择性膦氢化反应

本文总结了过去几十年特别是近15年来过渡金属催化下各种含磷-氢键的膦氢化合物对炔烃的高选择性膦氢化反应,详尽叙述了其发现、发展和现状.自1996年来,过渡金属催化高选择性膦氢化反应研究工作发展迅速,各种高选择性膦氢化反应不断开发,目前已具有底物适用范围广、过渡金属催化剂活性高、反应选择性高、原子经济性高、以及能满足不同合成需求等优点,并逐步向反应条件温和化、金属催化剂简单化、无配体化、合成步骤简易化以及原料催化剂成本低价化方向发展.虽然如此,至今仍缺乏关于本研究全面的综述和介绍,希望本文可以弥补文献缺陷,对过渡金属催化高选择性膦氢化反应研究有个客观全面的介绍.过渡金属催化烯烃的不对称膦氢化反应合成碳手性或磷手性的光学活性有机磷化合物作为相关研究中的起步最晚的分支,本文也将作阶段小结.     

超临界二氧化碳介质中的过渡金属催化反应

主要综述了以超临界二氧化碳作为反应介质的过渡金属催化加氢、羰基化、Heck和Stille反应的最新研究进展。     

Gold metal-catalyzed reactions of isocyanides with primary amines and oxygen: analogies with reactions of isocyanides in transition metal complexes

Despite its generally poor catalytic properties, bulk gold metal is observed to catalyze reactions of isocyanides (CN-R) with primary amines (H2N-R') and O2 to give carbodiimides (R-N=C=N-R') at room temperature and above. Detailed infrared reflection absorption spectroscopic (IRRAS) and kinetic studies show that the reaction occurs by initial eta1-adsorption of the isocyanide on the Au surface, which activates the isocyanide to attack by the amine. This attack is the rate-determining step in the catalytic cycle and has characteristics very similar to those of amine reactions with coordinated isocyanides in transition metal complexes. However, the metallic Au surface provides a pathway involving O2 to give the carbodiimide product whereas homogeneous metal ion catalysts give formamidines [HC(=NR)(NHR')].     

Transition metal-catalyzed organic reactions in undivided electrochemical cells

Transition metal-catalyzed organic electrochemistry is a rapidly growing research area owing in part to the ability of metal catalysts to alter the selectivity of a given transformation. This conversion mainly focuses on transition metal-catalyzed anodic oxidation and cathodic reduction and great progress has been achieved in both areas. Typically, only one of the half-cell reactions is involved in the organic reaction while a sacrificial reaction occurs at the counter electrode, which is inherently wasteful since one electrode is not being used productively. Recently, transition metal-catalyzed paired electrolysis that makes use of both anodic oxidation and cathodic reduction has attracted much attention. This perspective highlights the recent progress of each type of electrochemical reaction and relatively focuses on the transition metal-catalyzed paired electrolysis, showcasing that electrochemical reactions involving transition metal catalysis have advantages over conventional reactions in terms of controlling the reaction activity and selectivity and figuring out that transition metal-catalyzed paired electrolysis is an important direction of organic electrochemistry in the future and offers numerous opportunities for new and improved organic reaction methods.

Transition metal-catalyzed organic electrochemistry is a rapidly growing research area owing in part to the ability of metal catalysts to alter the selectivity of a given transformation.     

Cyclodextrins and their applications in aqueous-phase metal-catalyzed reactions

During these last years, cyclodextrins have greatly contributed to the development of catalytic processes in water. These cyclic oligosaccharides composed of 6(α), 7(β) or 8(γ) glucopyranose units improve the mass transfer in aqueous-organic two-phase systems and are useful compounds to design new catalysts. Thus, chemically modified cyclodextrins can be used to: (1) significantly increase the rate and selectivity of reactions catalyzed by water-soluble organometallic complexes; (2) design new water-soluble ligands for aqueous organometallic catalysis; (3) stabilize catalytically active noble metal nanoparticles in water; (4) facilitate reactions catalyzed by supported metals or metallic powder in water.     

溴代烯烃在金属催化偶联反应中的应用

溴代烯烃是一类重要的有机合成中间体,通过金属催化的偶联反应可以有效地形成碳-碳及碳-杂键.本文综述了溴代烯烃在金属催化偶联反应中应用的最新进展.     

Direct transition metal-catalyzed functionalization of heteroaromatic compounds

During the last two decades there has been considerable growth in the development of catalytic reactions capable of activating unreactive C-H bonds. These methods allow for the synthesis of complex molecules from easily available and cheaper precursors in a fewer number of steps. Naturally, the development of C-H activation methods for direct functionalization of heterocyclic molecules, invaluable building blocks for pharmaceutical and synthetic chemistry and material science, has received substantial attention as well. This critical review summarizes the progress made in this field until November 2006 (117 references).     

Three-component cycloadditions: the first transition metal-catalyzed [5+2+1] cycloaddition reactions

Prompted by our studies of transition metal-catalyzed [4+4], [4+2], [5+2], and [6+2] cycloadditions and by the view that these two-component reactions could be intercepted by a third component of one or more atoms, a new three-component transition metal-catalyzed cycloaddition is described. This new [5+2+1] cycloaddition proceeds in good to excellent yield and with high or complete regioselectivity with a variety of carbonyl-substituted alkynes to give bicyclo[3.3.0]octenone adducts, resulting from transannular closure of the intermediate eight-membered-ring cycloadduct. Effects of concentration, temperature, pressure, and catalyst loading on the efficiency of the reaction are discussed. This process provides access to complex building blocks for synthesis based on simple, readily available components.     

超临界二氧化碳介质中过渡金融催化反应研究进展

超临界介质中的化学反应研究是目前热点研究领域之一，对超临界CO2介质中 过渡金属催化反应研究进行了总结和述评，同时讨论了有关提高过渡金属催化剂在 超临界CO2中溶液度的方法。     

过渡金属催化喹唑啉酮衍生物的合成研究进展

针对当前报道较多的几种过渡金属催化喹唑啉酮合成新方法的研究进展进行了简要介绍.指出喹唑啉酮衍生物具有多种生物活性,在医药、农药等方面得到了广泛的应用;该类化合物的合成研究是当前的热点之一,尤其是过渡金属催化的喹唑啉酮的合成方法具有简单、直接、高效等优点,近年来发展迅速.     

First total synthesis of the neuronal cell protecting carbazole alkaloid carbazomadurin A by sequential transition metal-catalyzed reactions

The highly oxygenated neuronal cell protecting carbazole alkaloid carbazomadurin A was synthesized in nine steps and 11% overall yield from isovanillic acid.     

Symmetrical bisquinolones via metal-catalyzed cross-coupling and homocoupling reactions

Functionalized 4,4'-bisquinolones can be efficiently synthesized by microwave-assisted palladium(0)-catalyzed one-pot borylation/Suzuki cross-coupling reactions or via nickel(0)-mediated homocouplings of 4-chloroquinolin-2(1H)-one precursors. Both methods are also applicable to other types of symmetrical biaryls.     

Recent advances in transition metal-catalyzed enantioselective hydrogenation of unprotected enamines

Transition metal-catalyzed enantioselective hydrogenation of enamines is undoubtedly a useful and environment-friendly method for the preparation of optically pure chiral amines and amine derivatives. Over the last few decades, the use of transition metal catalysts containing chiral phosphorus or phosphine-oxazoline ligands attracted much attention for the hydrogenation of unprotected enamines. A number of efficient chiral catalysts have been developed, and some of them have shown high potential for the application in the synthesis of optical chiral amines in both laboratory and industry. This tutorial review focuses on the contributions concerning the transition metal-catalyzed enantioselective hydrogenation of unprotected enamines for the synthesis of chiral amines and amine derivatives.     

过渡金属催化1,2,4-三唑衍生物的合成研究进展

1,2,4-三唑衍生物在医药、农药、功能性材料等多领域应用广泛,该类化合物的合成也成为当前的热点之一,尤其是过渡金属催化1,2,4-三唑的合成具有简单、直接、高效等优点,近年来发展迅速.本文针对当前报道较多的几种过渡金属催化1,2,4-三唑合成新方法的研究进展进行了简要介绍.     

Polyaniline-supported nano metal-catalyzed coupling reactions: Opportunities and challenges

Polyanilines (PANIs) can be easily prepared from the available and cheap anilines via the oxidative polymerization reactions. Owing to the coordination of nitrogen in the material with metals, PANIs are widely used as the support of nano metal catalysts. In comparison with inorganic supports, the nano metals on PANIs were firmly anchored via the coordination bond so that they are not easily to lose during the reaction process. Moreover, since PANIs are versatile materials and their chemical features can be adjusted by introducing functional groups onto the monomers, the catalytic activities of the prepared catalysts are tunable. During the past decade, PANIs-supported nano metal catalysts have been widely applied in a variety of coupling reactions. This review aims to summarize the recent advances and give a perspective.