N-杂环卡宾催化选择性有机反应的新进展

近年来,有关N-杂环卡宾(NHC)的合成、催化性能及其应用得到了快速发展,特别是在催化选择性有机反应领域,NHC类催化剂显示出催化效率高、选择性好及性能优异等特点,而引起人们极大的关注。 本文从区域选择性、顺反异构选择性及手性选择性等方面综述了NHC催化选择性有机反应的最新进展,并予以了展望。     

The designing strategies of graphene-based peroxidase mimetic materials

Natural enzymes have been praised highly as ideal catalysts, presumably owing to their remarkable advantages of high efficiency, high selectivity, and mild reaction conditions. The reports of chemical simulation and systematic synthesis of natural enzymes such as peroxidase (POD) are rare because of their complex biological structures. POD represents a large family of oxidoreductases and offers a wide range of applications in many fields of science. Recent advance in the fusion of nanomaterial, catalysis, and biochemistry has inspired the development of artificial enzymes implemented with desired catalytic features of natural enzymes. Herein, we review the redox chemistry of POD and compare its catalytic performance to graphene-based nanomaterials (G-NMs) as POD mimetic nanoenzymes bases on catalytic center, binding site, and carrier function. Based on the viewpoints of stereo chemistry and molecular kinetic and dynamics in heterogeneous system, we evaluate and compare the suitability of different NMs as artificial enzyme constituent. We propose that reevaluates design strategies of graphene-based peroxidase (G-POD) mimetic materials and emphasizes on their selectivity (role as catalytic center, binding site, or carrier) is of uttermost.     

Energy-Efficient coaromatization of methane and propane (Special column of methane transformation, Review)

Development of highly effective catalysts for one-stage conversion of methane with high selectivity to valuable products and energy efficiency will provide an efficient way to utilize natural gas and oil-associated gases and to protect environment. In recent years, there have been many efforts on direct catalytic transformations of methane into higher hydrocarbons by feeding additives together with methane under non-oxidative conditions. This paper reviewed the advances in recent research on non-oxidative aromatization of methane in the presence of propane over different modified HZSM-5 catalysts. The thermodynamic consideration, the isotope verification and the mechanism of the activation of methane in the presence of propane are discussed in the paper in detail.     

Plasmonic heterogeneous catalysis for organic transformations

Plasmonic catalysis has been recognised as a promising alternative to many conventional thermal catalytic processes in organic synthesis. In addition to their high activity in fine chemical synthesis, plasmonic photocatalysts are also able to maintain control of selectivity under mild conditions by utilising visible-light as an energy source. This review provides an overview of the recent advances in organic transformations with plasmonic metal nanostructures, including selective reduction, selective oxidation, cross-coupling and addition reactions. We also summarize the photocatalysts and catalytic mechanisms involving surface plasmon resonance. Finally, control of reaction pathway and strategies for tailoring product selectivity in fine chemical synthesis are discussed.     

Promiscuous catalysis by the tetrahymena group I ribozyme

Catalytic promiscuity, the ability of an enzyme to catalyze alternative reactions, has been suggested to have played an important role in the evolution of new catalytic activities in protein enzymes. Similarly, promiscuous activities may have been advantageous in an earlier RNA world. The Tetrahymena Group I ribozyme naturally catalyzes the site-specific guanosine attack on an anionic phosphate diester and has been shown to also catalyze aminoacyl transfer to water, albeit with a small rate acceleration (<10-fold). This inefficient catalysis could be due to the differences in charge and/or geometry requirements for the two reactions. Herein, we describe a new promiscuous activity of this ribozyme, the site-specific guanosine attack on a neutral phosphonate diester. This alternative substrate lacks the negative charge at the reaction center but, in contrast to the aminoacyl substrate, can undergo nucleophilic attack with the same geometry as the natural substrate. Our results show that the neutral phosphonate reaction is catalyzed about 1 x 106-fold, substantially better than the acyl transfer but far below the normal anionic substrate. We conclude that both charge and geometry are important factors for catalysis of the normal reaction and that promiscuous catalytic activities of ribozymes could have been created or enhanced by reorienting and swapping RNA domains.     

Single-atom catalysis for organic reactions

Metal-based catalysis, including homogeneous and heterogeneous catalysis, plays a significant role in the modern chemical industry. Heterogeneous catalysis is widely used due to the high efficiency, easy catalyst separation and recycling. However, the metal-utilization efficiency for conventional heterogeneous catalysts needs further improvement compared to homogeneous catalyst. To tackle this, the pursing of heterogenizing homogeneous catalysts has always been attractive but challenging. As a recently emerging class of catalytic material, single-atom catalysts (SACs) are expected to bridge homogeneous and heterogeneous catalytic process in organic reactions and have arguably become the most active new frontier in catalysis field. In this review, a brief introduction and development history of single-atom catalysis and SACs involved organic reactions are documented. In addition, recent advances in SACs and their practical applications in organic reactions such as oxidation, reduction, addition, coupling reaction, and other organic reactions are thoroughly reviewed. To understand structure-property relationships of single-atom catalysis in organic reactions, active sites or coordination structure, metal atom-utilization efficiency (e.g., turnover frequency, TOF calculated based on active metal) and catalytic performance (e.g., conversion and selectivity) of SACs are comprehensively summarized. Furthermore, the application limitations, development trends, future challenges and perspective of SAC for organic reaction are discussed.     

Catalytic promiscuity in biocatalysis: using old enzymes to form new bonds and follow new pathways

Biocatalysis has expanded rapidly in the last decades with the discoveries of highly stereoselective enzymes with broad substrate specificity. A new frontier for biocatalysis is broad reaction specificity, where enzymes catalyze alternate reactions. Although often under-appreciated, catalytic promiscuity has a natural role in evolution and occasionally in the biosynthesis of secondary metabolites. Examples of catalytic promiscuity with current or potential applications in synthesis are reviewed here. Combined with protein engineering, the catalytic promiscuity of enzymes may broadly extend their usefulness in organic synthesis.     

An Efficient Solid-state Synthesis of 2-Thio-4-imidazolidinone Derivatives

In recent years increasingly intense interest has been directed towards the generation of small organic molecules by solid-state reactions, which has many advantages over conventional solution phase synthesis such as high efficiency and selectivity, easy separation and purification and environmental acceptability.     

Recent developments in olefin cross-metathesis

Among the many types of transition-metal-catalyzed C-C bond-forming reactions, olefin metathesis has come to the fore in recent years owing to the wide range of transformations that are possible with commercially available and easily handled catalysts. Consequently, olefin metathesis is now widely considered as one of the most powerful synthetic tools in organic chemistry. Until recently the intermolecular variant of this reaction, cross-metathesis, had been neglected despite its potential. With the evolution of new catalysts, the selectivity, efficiency, and functional-group compatibility of this reaction have improved to a level that was unimaginable just a few years ago. These advances, together with a better understanding of the mechanism and catalyst-substrate interactions, have brought us to a stage where more and more researchers are employing cross-metathesis reactions in multistep procedures and in the synthesis of natural products. The recent inclusion of alkynes and hindered bicyclic olefins as viable substrates for bimolecular metathesis coupling, the discovery of enantioselective cross-metathesis and cross-metathesis in water, and the successful marriage of metathesis and solid-phase organic synthesis has further widened the scope of this versatile reaction.     

Enantiocomplementary Epoxidation Reactions Catalyzed by an Engineered Cofactor-Independent Non-natural Peroxygenase

Peroxygenases are heme-dependent enzymes that use peroxide-borne oxygen to catalyze a wide range of oxyfunctionalization reactions. Herein, we report the engineering of an unusual cofactor-independent peroxygenase based on a promiscuous tautomerase that accepts different hydroperoxides (t-BuOOH and H₂O₂) to accomplish enantiocomplementary epoxidations of various α,β-unsaturated aldehydes (citral and substituted cinnamaldehydes), providing access to both enantiomers of the corresponding α,β-epoxy-aldehydes. High conversions (up to 98 %), high enantioselectivity (up to 98 % ee), and good product yields (50–80 %) were achieved. The reactions likely proceed via a reactive enzyme-bound iminium ion intermediate, allowing tweaking of the enzyme's activity and selectivity by protein engineering. Our results underscore the potential of catalytic promiscuity for the engineering of new cofactor-independent oxidative enzymes.     

Review of the aldol reaction

Aldol condensation is an important synthetic method widely used in organic synthesis. Development of catalytic methods that avoids the production of stoichiometric by-products while maintaining high levels of control available from stoichiometric processes provides an atom-economical alternative for these important transformations. Indeed, numerous catalysts for the aldol reaction have been reported in recent years, including enzymes, catalytic antibodies, organometals, organocatalysts, and small molecules. The direct aldol reaction is the most important reaction employed by synthetic chemists and is common in nature. Recently, various Lewis acids have been examined as catalysts for aldol reactions, but aldol condensation in a micellar medium has not been studied in detail so far. Because of stronger environmental concerns, organic reactions in green media, especially in water, have attracted more attention. It is believed that micelles act as nano reactors to enhance the reaction rates and give very good to excellent yields of end products.     

Recent Insights into Cu-Based Catalytic Sites for the Direct Conversion of Methane to Methanol

Direct conversion of methane to methanol is an effective and practical process to improve the efficiency of natural gas utilization. Copper (Cu)-based catalysts have attracted great research attention, due to their unique ability to selectively catalyze the partial oxidation of methane to methanol at relatively low temperatures. In recent decades, many different catalysts have been studied to achieve a high conversion of methane to methanol, including the Cu-based enzymes, Cu-zeolites, Cu-MOFs (metal-organic frameworks) and Cu-oxides. In this mini review, we will detail the obtained evidence on the exact state of the active Cu sites on these various catalysts, which have arisen from the most recently developed techniques and the results of DFT calculations. We aim to establish the structure–performance relationship in terms of the properties of these materials and their catalytic functionalities, and also discuss the unresolved questions in the direct conversion of methane to methanol reactions. Finally, we hope to offer some suggestions and strategies for guiding the practical applications regarding the catalyst design and engineering for a high methanol yield in the methane oxidation reaction.     

高通量筛选策略在细胞色素P450单加氧酶定向进化中的应用

细胞色素P450单加氧酶具有催化活性混杂性的特点,可以催化多种氧化反应,因而在生物催化领域受到了极大的关注。然而P450单加氧酶往往存在催化活性低、稳定性差、区域和立体选择性不理想等问题,从而限制了其在生物催化领域的广泛运用。蛋白质定向进化的发展与运用为改善P450单加氧酶的催化性能提供了有效的途径,而一种高效的高通量筛选策略是保证酶蛋白定向进化成功实施的关键。本文综述了P450单加氧酶定向进化过程中高通量筛选策略的最新进展。     

Recent trends in synthetic strategies using magnetic nanostructures as green catalysts in synthesis of pyran analogues

In recent years, magnetic nanoparticles and nanocomposites play an important role as a nanocatalyst in the creation of a wide range of bioactive heterocycles with extraordinarily high activity and selectivity, low energy consumption, and extended life. Among all heterocycles, many natural products, pharmaceuticals, and bioactive compounds contain pyran scaffolds which have a wide range of uses in biomedical research, industry, and medicine. Additionally, these are also widely used in the synthesis of novel heterocyclic systems as precursors. This study focused on recent advances in the last 5 years in using various magnetic recoverable and recycled nanoparticles and nanocomposites to synthesize pyran derivatives and their pharmacological activity. This article has been classified into three subsections: (i) MNPs-metal nanocomposite catalyzed reactions, (ii) MNPs-organic based nanocomposite catalyzed reactions, and (iii) MNPs-ionic liquid nanocomposite catalyzed reactions and (iv) MNPs-acid based nanocomposite to describe catalytic efficiency of magnetic nanocomposites for the synthesis of pyran derivatives. A comparative study of nanocomposites and different approaches for green synthesis of pyrans by highlighting the advantages and disadvantages along with catalyst recovery and recyclability has been mentioned, which will help scientists to probe and stimulate the study of these scaffolds.     

Enantiocomplementary Epoxidation Reactions Catalyzed by an Engineered Cofactor‐Independent Non‐natural Peroxygenase

Peroxygenases are heme‐dependent enzymes that use peroxide‐borne oxygen to catalyze a wide range of oxyfunctionalization reactions. Herein, we report the engineering of an unusual cofactor‐independent peroxygenase based on a promiscuous tautomerase that accepts different hydroperoxides (t‐BuOOH and H₂O₂) to accomplish enantiocomplementary epoxidations of various α,β‐unsaturated aldehydes (citral and substituted cinnamaldehydes), providing access to both enantiomers of the corresponding α,β‐epoxy‐aldehydes. High conversions (up to 98 %), high enantioselectivity (up to 98 % ee), and good product yields (50–80 %) were achieved. The reactions likely proceed via a reactive enzyme‐bound iminium ion intermediate, allowing tweaking of the enzyme's activity and selectivity by protein engineering. Our results underscore the potential of catalytic promiscuity for the engineering of new cofactor‐independent oxidative enzymes.     

Catalytic asymmetric aldol reactions in aqueous media

Nature has perfected the stereospecific aldol reaction by using aldolase enzymes. While virtually all the biochemical aldol reactions use unmodified donor and acceptor carbonyls and take place under catalytic control in an aqueous environment, the chemical domain of the aldol addition has mostly relied on prior transformation of carbonyl substrates, and the whole process traditionally is carried out in anhydrous solvents. The area of aqua-asymmetric aldol reactions has received much attention recently in light of the perception both of its green chemistry advantages and its analogy to eon-perfected enzyme catalysis. Both chiral metal complexes and small chiral organic molecules have been recently reported to catalyze aldol reactions with relatively high chemical and stereochemical efficiency. This tutorial review describes recent developments in this area.     

Visible-Light-Induced Catalytic Selective Halogenation with Photocatalyst

Halide moieties are essential structures of compounds in organic chemistry due to their popularity and wide applications in many fields such as natural compounds, agrochemicals, and pharmaceuticals. Thus, many methods have been developed to introduce halides into various organic molecules. Recently, visible-light-driven reactions have emerged as useful methods of organic synthesis. Particularly, halogenation strategies using visible light have significantly improved the reaction efficiency and reduced toxicity, as well as promoted reactions under mild conditions. In this review, we have summarized recent studies in visible-light-mediated halogenation (chlorination, bromination, and iodination) with photocatalysts.     

A stereoselective vanadium-dependent chloroperoxidase in bacterial antibiotic biosynthesis

Halogenases catalyze reactions that introduce halogen atoms into electron-rich organic molecules. Vanadium-dependent haloperoxidases are generally considered to be promiscuous halogenating enzymes that have thus far been derived exclusively from eukaryotes, where their cellular function is often disputed. We now report the first biochemical characterization of a bacterial vanadium-dependent chloroperoxidase, NapH1 from Streptomyces sp. CNQ-525, which catalyzes a highly stereoselective chlorination-cyclization reaction in napyradiomycin antibiotic biosynthesis. This finding biochemically links a vanadium chloroperoxidase to microbial natural product biosynthesis.     

Suzuki Coupling Reactions in Neat Water as the Solvent: Where in the Biphasic Reaction Mixture Do the Catalytic Reaction Steps Occur?

Many reports on water‐compatible palladium catalysts have appeared in the recent literature. For hydrophobic substrates, mixtures with pure water are biphasic, and it is widely not regarded that the elusive locality of the catalytic process (in water, the organic layer, or at the phase boundary) has an important impact on the mechanism and efficiency of the reaction. In the present work, for the first time systematic variation of reaction parameters has been performed for Suzuki coupling experiments with chloro‐ and bromoarenes in pure water. The investigations are not only aimed at the factors influencing the catalytic activity, but also at the effects that may occur particularly in water/organic biphasic media, and on the question as to in which of the two liquid phases the reaction takes place. These investigations have revealed that dilution of the base (in the aqueous layer) and the Pd species (in the organic layer) are detrimental to the reaction, and that phase‐transfer processes play a major role in the overall mechanism. A series of experiments with variation of parameters like precatalyst hydrophilicity, organic and water phase volume, additives, stirring rate, base concentration, and so forth, indicate that for the systems under study the reaction occurs in the organic layer. The water phase needs to be present to dissolve and provide polar reactants, and re‐absorb side products. The results encourage to pay more regard to the question of phase locality of coupling reactions in water in general.     

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.