Conjugated Microporous Polymers for Heterogeneous Catalysis

Conjugated microporous polymers (CMPs) are a class of crosslinked polymers that combine permanent micropores with π‐conjugated skeletons and possess three‐dimensional (3D) networks. Compared with conventional materials such as metal–organic frameworks (MOFs) and covalent organic frameworks (COFs), CMPs usually have superior chemical and thermal stability. CMPs have made significant progress in heterogeneous catalysis in the past seven years. With a bottom‐up strategy, catalytic moieties can be directly introduced into in the framework to produce heterogeneous CMP catalysts. Higher activity, stability, and selectivity can be obtained with heterogeneous CMP catalysts in comparison with their homogeneous analogs. In addition, CMP catalysts can be easily isolated and recycled. In this review, we focus on CMPs as an intriguing platform for developing various highly efficient and recyclable heterogeneous catalysts in organic reactions. The design, synthesis, and structure of these CMP catalysts are also discussed in this focus review.     

Catalysis in Single Crystalline Materials: From Discrete Molecules to Metal-Organic Frameworks

Catalysis is one of the key techniques for people's modern life. It has created numerous essential chemicals such as biomedicines, agricultural chemicals and unique materials. Heterogeneous catalysis is the new emerging method with reusable catalysts. Among heterogenous catalysis patterns developed so far, single crystalline catalysis has become the promising one owing to its high catalytic density and selectivity resulted by the inherent porosity, orderliness of the lattices and permeability. These crystalline catalysts could be used in various reactions such as photo-dimerization, Diels-Alder reaction, CO₂ transformation and so on. In this review, we highlighted the reported works about the single crystalline catalysts. Both discrete small molecules and metal-organic frameworks (MOFs) have been used to prepare single crystals for catalysis. For discrete molecules based crystalline catalysts, coordinated and covalent molecules have been used. There were more catalytic modes in crystalline MOF catalysts. Three patterns were identified in this review: single crystalline MOFs i) without catalytic sites, ii) with inherent catalytic features and iii) with introducing catalytic units by post synthetic modification. Based on these examples, this review committed to provide the inspirations for the further design and application of single crystalline materials.     

Potential Utilization of Metal–Organic Frameworks in Heterogeneous Catalysis: A Case Study of Hydrogen‐Bond Donating and Single‐Site Catalysis

Crystalline solid materials are platforms for the development of effective catalysts and have shown vast benefits at the frontiers between homogeneous and heterogeneous catalysts. Typically, these crystalline solid catalysts outperformed their homogeneous analogs due to their high stability, selectivity, better catalytic activity, reusability and recyclability in catalysis applications. This point of view, comprising significant features of a new class of porous crystalline materials termed as metal‐organic frameworks (MOFs) engendered the attractive pathway to synthesize functionalized heterogeneous MOF catalysts. The present review includes the recent research progress in developing both hydrogen‐bond donating (HBD) MOF catalysts and MOF‐supported single‐site catalysts (MSSCs). The first part deals with the novel designs of urea‐, thiourea‐ and squaramide‐containing MOF catalysts and study of their crucial role in HBD catalysis. In the second part, we discuss the important classification of MSSCs with existing examples and their use in desired catalytic reactions. In addition, we describe the relative catalytic efficiency of these MSSCs with their homogeneous and similarly reported analogs. The precise knowledge of discussed heterogeneous MOF catalysts in this review may open the door for new research advances in the field of MOF catalysis.     

Unveiling the Local Structure of Palladium Loaded into Imine‐Linked Layered Covalent Organic Frameworks for Cross‐Coupling Catalysis

Layered covalent organic frameworks (2D‐COFs), composed of reversible imine linkages and accessible pores, offer versatility for chemical modifications towards the development of catalytic materials. Nitrogen‐enriched COFs are good candidates for binding Pd species. Understanding the local structure of reacting Pd sites bonded to the COF pores is key to rationalize interactions between active sites and porous surfaces. By combining advanced synchrotron characterization methods with periodic computational DFT modeling, the precise atomic structure of catalytic Pd sites attached to local defects is resolved within an archetypical imine‐linked 2D‐COF. This material was synthesized using an in situ method as a gel, under which imine hydrolysis and metalation reactions are coupled. Local defects formed in situ within imine‐linked 2D‐COF materials are highly reactive towards Pd metalation, resulting in active materials for Suzuki–Miyaura cross‐coupling reactions.     

Metal‐Free Boron‐Containing Heterogeneous Catalysts

Metal‐free catalysts have distinct advantages over metal and metal oxide catalysts, such as lower cost as well as higher reliability and sustainability. Among the nonmetal compounds used in catalysis, boron‐containing compounds with a few unique properties have been developed. In this Minireview, the recent advances in the field of boron‐containing metal‐free catalysts are presented, including binary and ternary boron‐containing catalytic materials. Additionally, the three main applications in catalysis are considered, namely, electrocatalysis, thermal catalysis, and photocatalysis, with the role of boron discussed in depth for each specific catalytic application. Boron‐containing compounds could have a substantial impact on the field of metal‐free catalysts in the future.     

共价有机框架材料在多相催化领域的研究进展（英文）

共价有机框架(COFs)材料是近年来在拓扑学基础上发展起来的一类新型有机多孔聚合物,是有机单体通过可逆共价键连接而形成的晶型多孔材料,具有拓扑结构"可设计"、比表面积大、结构规整、孔道均一、孔径可调节以及易于修饰和功能化等优点.与金属有机框架材料(MOFs)相比,由于COFs是以共价键连接形成空间网络结构,具有较好的热稳定性和化学稳定性,又被称为"有机分子筛".COFs的构筑单体为有机小分子,有机小分子来源广泛而且种类繁多,使得构筑单体多样化,便于通过构筑单体来调控目标材料的结构和功能.自2005年首次报道以来,COFs以其独特的结构和优越的性能,吸引了广大科研工作者的极大兴趣,对其结构设计、可控合成、结构解析以及功能探索成为了研究热点,在气体吸附与分离、光电材料等领域展现出了广阔的应用前景.特别是在催化领域,由于COFs材料的多孔性、敞开的孔道结构、良好的稳定性以及易于修饰的特点,采用COFs作为催化剂以及催化剂载体受到了人们普遍的关注.作为催化剂,COFs可分为本征型催化剂和负载型催化剂.本征型催化剂的设计方法是基于"自下而上"策略将催化活性中心嵌入材料骨架之中;负载型催化剂的设计方法是以COFs为载体,通过后修饰方式负载金属颗粒或离子来构建多相催化剂.本征型COFs催化剂是在分子水平上引入催化活性中心,具有活性位点均匀分散、数量可控的特点,而且COFs规整均一的孔道结构有利于底物的传质,也为择形催化提供了可能;负载型催化剂通过后修饰方式引入催化活性中心,由于COFs以共价键连接,催化剂稳定性较高.COFs载体具有较大的比表面积,使得催化活性位点分散性好,也有利于底物与催化活性位点的结合.本文综述了COFs作为多相催化剂在催化领域的发展状况,按照COFs引入催化活性位点的类别,如单催化位点、双催化位点以及负载的金属纳米粒子进行了细致的阐述,重点讨论了COFs催化剂的设计理念、制备方式、功能化策略、材料的稳定性、催化活性以及选择性等内容.此外,对COFs作为光催化剂以及电催化剂方面的研究也进行了详细的介绍.最后,我们讨论了COFs在未来催化领域所面临的问题及挑战,并展望了COFs在超分子催化以及酶催化等方面的应用前景.     

Substrate‐Selective Catalysis

Substrate selectivity is an important output function for the validation of different enzyme models, catalytic cavity compounds, and reaction mechanisms as demonstrated in this review. In contrast to stereo‐, regio‐, and chemoselective catalysis, the field of substrate‐selective catalysis is under‐researched and has to date generated only a few, but important, industrial applications. This review points out the broad spectrum of different reaction types that have been investigated in substrate‐selective catalysis. The present review is the first one covering substrate‐selective catalysis and deals with reactions in which the substrates involved have the same reacting functionality and the catalysts is used in catalytic or in stoichiometric amounts. The review covers real substrate‐selective catalysis, thus only including cases in which substrate‐selective catalysis has been observed in competition between substrates.     

Homochiral Covalent Organic Frameworks for Asymmetric Catalysis

Owing to their permanent porosity, highly ordered and extended structure, good chemical stability, and tunability, covalent organic frameworks (COFs) have emerged as a new type of organic materials that can offer various applications in different fields. Benefiting from the huge database of organic reactions, the required functionality of COFs can be readily achieved by modification of the corresponding organic functional groups on either polymerizable monomers or established COF frameworks. This striking feature allows homochiral covalent organic frameworks (HCCOFs) to be reasonably designed and synthesized, as well as their use as a unique platform to fabricate asymmetric catalysts. This contribution provides an overview of new progress in HCCOF-based asymmetric catalysis, including design, synthesis, and their application in asymmetric organic synthesis. Moreover, major challenges and developing trends in this field are also discussed. It is anticipated that this review article will provide some new insights into HCCOFs for heterogeneous asymmetric catalysis and help to encourage further contributions in this young but promising field.     

Sophisticated Design of Covalent Organic Frameworks with Controllable Bimetallic Docking for a Cascade Reaction

Precise control of the number and position of the catalytic metal ions in heterogeneous catalysts remains a big challenge. Here we synthesized a series of two‐dimensional (2D) covalent organic frameworks (COFs) containing two different types of nitrogen ligands, namely imine and bipyridine, with controllable contents. For the first time, the selective coordination of the two nitrogen ligands of the 2D COFs to two different metal complexes, chloro(1,5‐cyclooctadiene)rhodium(I) (Rh(COD)Cl) and palladium(II) acetate (Pd(OAc)₂), has been realized using a programmed synthetic procedure. The bimetallically docked COFs showed excellent catalytic activity in a one‐pot addition–oxidation cascade reaction. The high surface area, controllable metal‐loading content, and predesigned active sites make them ideal candidates for their use as heterogeneous catalysts in a wide range of chemical reactions.     

Searching for New Reactivity (Nobel Lecture)

The processes for the selective oxidation of olefins have long been among the most useful tools for day‐to‐day organic synthesis. Herein, the focus is on the asymmetric‐epoxidation (AE) and asymmetric‐dihydroxylation (AD) reactions developed by Sharpless and co‐workers. The reactions have a wide scope, are simple to run, and involve readily available starting materials. Ligand‐accelerated catalysis is crucial to these reactions and might be the agent for uncovering more catalytic processes. In addition to the selectivity benefits of catalysis, the phenomenon of turnover (amplification) raises its potential impact. The author and his co‐workers developed small, highly enantioselective catalysts that were unfettered by the “lock‐and‐key” selectivity of Natures enzymes, and tolerant of substrates throughout the entire range of olefin substitution patterns.     

Catalytic Selective Synthesis

Complete control of the product of a catalytic reaction can be achieved on the basis of catalyst structure, even when the reaction conditions are nearly identical. Catalyst‐controlled selectivity is well established for enantioselective catalysis but less formulated for catalytic regio‐, chemo‐, or product‐selective reactions. This Review describes selective transformations of the same starting materials into two or more different products simply by the choice of catalyst. By collecting and highlighting examples of selective catalysis, we hope that the field will be encouraged by the progress that has been made while bringing attention to unmet needs in the design and mechanistic understanding of selective catalysts.     

Magnetically Separable Nanocatalysts: Bridges between Homogeneous and Heterogeneous Catalysis

Recovery and reuse of expensive catalysts after catalytic reactions are important factors for sustainable process management. The aim of this Review is to highlight the progress in the formation and catalytic applications of magnetic nanoparticles and magnetic nanocomposites. Directed functionalization of the surfaces of nanosized magnetic materials is an elegant way to bridge the gap between heterogeneous and homogeneous catalysis. The introduction of magnetic nanoparticles in a variety of solid matrices allows the combination of well‐known procedures for catalyst heterogenization with techniques for magnetic separation.     

3D Microporous Base‐Functionalized Covalent Organic Frameworks for Size‐Selective Catalysis

The design and synthesis of 3D covalent organic frameworks (COFs) have been considered a challenge, and the demonstrated applications of 3D COFs have so far been limited to gas adsorption. Herein we describe the design and synthesis of two new 3D microporous base‐functionalized COFs, termed BF‐COF‐1 and BF‐COF‐2, by the use of a tetrahedral alkyl amine, 1,3,5,7‐tetraaminoadamantane (TAA), combined with 1,3,5‐triformylbenzene (TFB) or triformylphloroglucinol (TFP). As catalysts, both BF‐COFs showed remarkable conversion (96 % for BF‐COF‐1 and 98 % for BF‐COF‐2), high size selectivity, and good recyclability in base‐catalyzed Knoevenagel condensation reactions. This study suggests that porous functionalized 3D COFs could be a promising new class of shape‐selective catalysts.     

Functionalized Silicas for Metal‐Free and Metal‐Based Catalytic Applications: A Review in Perspective of Green Chemistry

Heterogeneous catalysis plays a key role in promoting green chemistry through many routes. The functionalizable reactive silanols highlight silica as a beguiling support for the preparation of heterogeneous catalysts. Metal active sites anchored on functionalized silica (FS) usually demonstrate the better dispersion and stability due to their firm chemical interaction with FSs. Having certain functional groups in structure, FSs can act as the useful catalysts for few organic reactions even without the need of metal active sites which are termed as the covetous reusable organocatalysts. Magnetic FSs have laid the platform where the effortless recovery of catalysts is realized just using an external magnet, resulting in the simplified reaction procedure. Using FSs of multiple functional groups, we can envisage the shortened reaction pathway and, reduced chemical uses and chemical wastes. Unstable bio‐molecules like enzymes have been stabilized when they get chemically anchored on FSs. The resultant solid bio‐catalysts exhibited very good reusability in many catalytic reactions. Getting provoked from the green chemistry aspects and benefits of FS‐based catalysts, we confer the recent literature and progress focusing on the significance of FSs in heterogeneous catalysis. This review covers the preparative methods, types and catalytic applications of FSs. A special emphasis is given to the metal‐free FS catalysts, multiple FS‐based catalysts and magnetic FSs. Through this review, we presume that the contribution of FSs to green chemistry can be well understood. The future perspective of FSs and the improvements still required for implementing FS‐based catalysts in practical applications have been narrated at the end of this review.     

Dual Gold Catalysis: σ,π‐Propyne Acetylide and Hydroxyl‐Bridged Digold Complexes as Easy‐To‐Prepare and Easy‐To‐Handle Precatalysts

A series of dinuclear gold σ,π‐propyne acetylide complexes were prepared and tested for their catalytic ability in dual gold catalysis that was based on the reaction of an electrophilic π‐complex of gold with a gold acetylide. The air‐stable and storable catalysts can be isolated as silver‐free catalysts in their activated form. These dual catalysts allow a fast initiation phase for the dual catalytic cycles without the need for additional additives for acetylide formation. Because propyne serves as a throw‐away ligand, no traces of the precatalyst are generated. Based on the fast initiation process, side products are minimized and reaction rates are higher for these catalysts. A series of test reactions were used to demonstrate the general applicability of these catalysts. Lower catalyst loadings, faster reaction rates, and better selectivity, combined with the practicability of these catalysts, make them ideal catalysts for dual gold catalysis.     

Stereoconvergent,Redox‐Neutral Access to Tetrahydroquinoxalines through Relay Epoxide Opening/Amination of Alcohols

We present an economical catalytic procedure to convert readily available 1,2‐diaminobenzenes and terminal epoxides into valuable 1,2,3,4‐tetrahydroquinoxalines in a highly enantioselective fashion. This procedure operates through relay zinc and iridium catalysis, and achieves redox‐neutral and stereoconvergent production of valuable chiral heterocycles from racemic starting materials with water as the only side product. The use of commercially available reagents and catalysts and a convenient procedure also make this catalytic method attractive for practical application.     

2020 Roadmap on two-dimensional nanomaterials for environmental catalysis

This roadmap demonstrates a series of two-dimensional nanomaterials, such as graphene, black phosphorus, oxides, layered double hydroxides, chalcogenides, bismuth-based layered compounds, MXenes, metal organic frameworks, covalent organic frameworks, and others, for environmental catalysis.     

碳催化剂在催化反应中的应用

由于碳材料表面存在缺陷,可生成具有不同性能的活性位,因此可催化不同的热催化反应.我们首先介绍了单质碳材料的表面结构化学:其表面活性位主要为含杂原子官能团;然后对其可催化的反应进行了介绍:碳单质材料可催化选择性氧化反应、高级氧化反应、还原反应、烷烃活化反应、酸催化反应、电催化还原和氧化反应等.对碳单质催化剂的制备方法、所催化的各类反应、催化活性位、催化效果及催化机理也进行了简介.单纯的碳材料并不能完全满足不同反应的催化要求,可通过掺杂杂原子、焙烧、酸处理等手段对碳催化剂进行改性,使其具有不同的催化性能.相信随着对碳催化认识的不断加深,碳催化的应用范围会越来越广,在不远的未来将应用于工业化生产.     

Mixed‐Ligand Catalysts: A Powerful Tool in Transition‐Metal‐Catalyzed Cross‐Coupling Reactions

Transition‐metal‐catalyzed cross‐coupling reactions have fundamentally revolutionized organic synthesis, empowering the otherwise difficult to achieve products with rapid and convenient accesses alongside excellent yields. Within these reactions, ligands often play a critical role in specifically and effectively advocating the corresponding catalysis. Consequently, a myriad of ligands have been created and applied to make a fine tuning of electronic and steric effect of catalysts, remarkably promoting catalytic efficiency and applicability. The “mixed‐ligand” concept has recently emerged; by combining and capitalizing on the superiority of each individual ligand already available, an expedient way can be achieved to reach a larger extent of catalytic diversity and efficacy. Given the availability of a wealth of ligands, it is reasonable to have great expectations for the original application of mixed‐ligand catalytic systems and their important value in organic synthesis.     

Iron‐Catalyzed Cross‐Couplings in the Synthesis of Pharmaceuticals: In Pursuit of Sustainability

The scarcity of precious metals has led to the development of sustainable strategies for metal‐catalyzed cross‐coupling reactions. The establishment of new catalytic methods using iron is attractive owing to the low cost, abundance, ready availability, and very low toxicity of iron. In the last few years, sustainable methods for iron‐catalyzed cross‐couplings have entered the critical area of pharmaceutical research. Most notably, iron is one of the very few metals that have been successfully field‐tested as highly effective base‐metal catalysts in practical, kilogram‐scale industrial cross‐couplings. In this Minireview, we critically discuss the strategic benefits of using iron catalysts as green and sustainable alternatives to precious metals in cross‐coupling applications for the synthesis of pharmaceuticals. The Minireview provides an essential introduction to the fundamental aspects of practical iron catalysis, highlights areas for improvement, and identifies new fields to be explored.