不对称催化剂在菊酸合成中的应用

不对称催化剂的研究,正引起有机化学家的兴趣。它能用于菊酸及其它化合物的不对称合成。也可将此类催化剂固定在高分子上作为非均相化催化剂使用。     

Microwave Assisting Solid Phase Organic Reactions-Approach to the Efficient Solid Phase Organic Synthesis

Solid phase organic synthesis provides a rapid mean for the preparation of compounds libraries, and has been successfully used for the construction of both oligometric compounds and small molecule compounds libraries^[1]. That leads the resurgence of interest in solid phase organic synthesis, which encourages organic chemists to develop new reliable reactions, linkers and analytical techniques.     

微波辅助组合合成的研究进展

微波辅助组合合成技术是近年来发展起来的一种新的制备化合物库的组合化学技术, 它不仅可以克服传统固相组合合成技术以及液相组合合成技术无法提高产物收率的不足, 而且利用该技术所制得的化合物库中对应的是高纯度的单一化合物, 采用高通量筛选技术可以快速直接地确定高活性结构, 极大地提高了新药开发的效率. 主要就近年来微波辅助组合合成技术的研究进展情况进行介绍, 内容包括固相组合合成、基于聚合物支载的催化剂的组合合成、液相组合合成、氟相组合合成以及组合平行合成等.     

Indenylmetal Catalysis in Organic Synthesis

Synthetic organic chemists have a long‐standing appreciation for transition metal cyclopentadienyl complexes, of which many have been used as catalysts for organic transformations. Much less well known are the contributions of the benzo‐fused relative of the cyclopentadienyl ligand, the indenyl ligand, whose unique properties have in many cases imparted differential reactivity in catalytic processes toward the synthesis of small molecules. In this Review, we present examples of indenylmetal complexes in catalysis and compare their reactivity to their cyclopentadienyl analogues, wherever possible.     

Transition Metals in the Synthesis and Functionalization of Indoles [New Synthesis Methods (72)]

The use of transition-metal complexes as reagents for the synthesis of complex organic compounds has been under development for at least several decades, and many extraordinary organic transformations of profound potential have been realized. However, adoption of this chemistry by the practicing synthetic organic chemist has been inordinately slow, and only now are transition-metal reagents beginning to achieve their rightful place in the arsenal of organic synthesis. Several factors contributed to the initial reluctance of synthetic organic chemists to use organometallic reagents. Lacking education and experience in the ways of elements having d electrons, synthetic chemists viewed organometallic processes as something mysterious and unpredictable, and not to be discussed in polite society. Organometallic chemists did not help matters by advertising their latest advances as useful synthetic methodology, but restricting their studies to very simple organic systems lacking any serious functionality (e.g., the “methyl, ethyl, butyl, futile” syndrome). Happily, things have changed. Organometallic chemists have turned their attention to more complex systems, and more recently trained organic chemists have benefited from exposure to the application of transition metals. This combination has set the stage for major advances in the use of transition metals in the synthesis of complex organic compounds. This review deals with one aspect of this area, the use of transition metals in the synthesis of indoles.     

Synthesis of 1,8-Dioxo-octahydroxanthene Derivatives Catalyzed by p-Dodecylbenezenesulfonic Acid in Water

With the increasing concerns of the environment, more and more chemists are devoted to the research of the "green synthesis" which means that the reagent, solvent and catalyst are environmentally friendly in the organic chemical reactions. The importance of aqueous reaction is now generally recognized, and development of carbon-carbon bond-forming reactions that can be carried out in aqueous media is now one of the most challenging topics in organic synthesis.[1]Herein, we report a clean synthesis of 3,3,6,6-tetramethyl-9-aryl-1,8-dioxo-octahydroxanthene derivatives from aromatic aldehyde and 5,5-dimethyl-1,3-cyclohexadione using p-dodecylbenezenesulfonic acid (DBSA) as the catalyst in water.This method provides several advantages such as high yield, simple work-up procedure and environmental friendliness and water was chosen as a green solvent. All the products were characterized by m.p., 1H NMR, IR and elemental analyses.     

Guest Editorial: The Professional Status of European Chemists and Chemical Engineers

Which country pays its chemists and chemical engineers the highest salaries? Where can I find a new job quickest? Which chemical sub‐discipline offers most jobs? Reliable answers for these and other questions have been derived from the first European employment survey for chemists and chemical engineers, which was carried out in 2013. Here we publish the first general evaluation of the results of this survey.     

β‐Cyclodextrin as an Efficient and Recyclable Supramolecular Catalyst for the Synthesis of Heterocyclic Compounds

β‐Cyclodextrin (β‐CD ), a naturally occurring supramolecular structure, is an effective catalyst for the synthesis of heterocyclic compounds. Its ubiquity, high performance, nontoxicity, ease of separation, and reusability have drawn the attention of green chemists. Here we present the synthetic procedures of heterocyclic compounds catalyzed by β‐CD in water and compare them with those using organic solvents. In many cases, using water as the solvent shows better efficiency than conventional organic solvents with regard to catalytic activity and simplicity of recycling procedures. This review highlights the applications of β‐CD in catalysis covering the years 2004–2016.     

Ionic liquid assisted synthesis of S-heterocycles

Some organic solvents are highly toxic, flammable, and even explosive. In particular, high vapor pressures and toxicity of certain volatile organic solvents may cause significant environmental problems. Therefore, alternative solvents or media with tunable and versatile solvation properties for conducting chemical reactions and materials synthesis have been actively sought. Ionic liquids have numerous applications not only as environmentally benign reaction media, but also as catalysts and reagents. Due to the increase of environmental consciousness in chemical research and industry, the challenge for a sustainable environment calls for clean procedures that avoid the use of harmful organic solvents. Due to the special properties of ILs (ionic liquids) such as wide liquid range, good solvating ability, negligible vapor pressure, non-inflammability, non-volatility, environment friendly medium, high thermal stability, good stability in air and moisture, easy recycling and rate promoters etc. they are used in organic synthesis. Therefore, ionic liquids have attracted the attention of chemists and act as catalyst and reaction medium in organic reactions with high activity. Highly efficient methods are explored for the preparation of S-heterocycles with the application of ILs as catalyst and reaction medium.     

对映选择性亲电氟化反应研究进展

含氟有机化合物, 特别是手性氟化物在医药、农药及功能性材料等相关领域的作用备受注目. 尽管在分子中有立体选择性地引入一个氟原子一直是有机化学家面临的一个挑战性问题, 近年来在化学家们的不断努力下, 对映选择性氟化反应研究取得重要进展. 高光学活性的手性氟化物可通过手性亲电氟化试剂诱导的立体选择性氟化反应, 基于底物的手性氟化反应以及手性催化剂诱导的不对称催化氟化反应等来制备. 特别是, 手性金属配合物和有机催化剂诱导的不对称催化氟化反应被广泛应用于各类手性氟化物的合成, 已成为不对称氟化反应研究的热点. 全面介绍对映选择性亲电氟化反应研究概况和最新进展, 讨论各种不对称氟化反应的特点及应用范围.     

Transition-metal-catalyzed cyclization reactions using vinyl and ethynyl benzoxazinones as dipole precursors

Vinyl and ethynyl benzoxazinones have recently received increasing attention from organic chemists because they are powerful tools for the construction of structurally diverse aza-heterocycles. A number of catalytic cyclization reactions have been developed that used these two reagents and required the presence of a transition-metal catalyst (i.e., palladium, iron, and copper). This review highlights the design and synthesis of these versatile reagents, and their applications as precursors for transition-metal-containing 1,4-dipoles in dipolar cyclizations and related cascade reactions. The general mechanisms and asymmetric inductions are briefly discussed as well.     

Supramolecular Hydrogels Made of Basic Biological Building Blocks

As a consequence of the self‐assembly of small organic molecules in water, supramolecular hydrogels are evolving from serendipitous events during organic synthesis to become a new type of materials that hold promise for applications in biomedicine. In this Focus Review, we describe recent advances in the use of basic biological building blocks for creating molecules that act as hydrogelators and the potential applications of the corresponding hydrogels. After introducing the concept of supramolecular hydrogels and defining the scope of this review, we briefly describe the methods for making and characterizing supramolecular hydrogels. We then discuss representative hydrogelators according to the categories of their building blocks, such as amino acids, nucleobases, and saccharides, and highlight the applications of the hydrogels when necessary. Finally, we offer our perspective and outlook on this fast‐growing field at the interface of organic chemistry, materials, biology, and medicine. By providing a snapshot for chemists, engineers, and medical scientists, we hope that this Focus Review will contribute to the development of multidisciplinary research on supramolecular hydrogels for a wide range of applications in different fields.     

Developing a Practical Chiral Toolbox for Asymmetric Catalytic Reactions

Chiral Quest's Toolbox Approach: During the last several decades, chemists have made major progress in discovering man-made catalysts to perform challenging asymmetric transformations. However, there is no universal chiral ligand or catalyst for solving problems in enantioselective transformations. The focus of Chiral Quest's research is to develop a useful chiral toolbox for strategically important asymmetric catalytic reactions by inventing a diverse set of novel chiral ligands and combining them with transition metals as effective enantioselective catalysts. The toolbox approach addresses significant problems in organic stereochemistry and has resulted in practical methods for the synthesis of chiral pharmaceuticals and agrochemicals     

Single-chain folding of polymers for catalytic systems in water

Enzymes are a source of inspiration for chemists attempting to create versatile synthetic catalysts. In order to arrive at a polymeric chain carrying catalytic units separated spatially, it is a prerequisite to fold these polymers in water into well-defined compartmentalized architectures thus creating a catalytic core. Herein, we report the synthesis, physical properties, and catalytic activity of a water-soluble segmented terpolymer in which a helical structure in the apolar core is created around a ruthenium-based catalyst. The supramolecular chirality of this catalytic system is the result of the self-assembly of benzene-1,3,5-tricarboxamide side chains, while the catalyst arises from the sequential ruthenium-catalyzed living radical polymerization of the different monomers followed by ligand exchange. The polymers exhibit a two-state folding process and show transfer hydrogenation in water.     

Ultrasound irradiation in heterocycle synthesis: An overview

The synthesis of heterocyclic compounds has been a hot topic for several decades. Synthetic organic chemists are always in search of new methodologies which are greener for the synthesis of heterocyclic compounds. The ultrasound-assisted reactions have contributed much to this field. This review focuses on the impact of sonochemistry in the synthesis of heterocyclic compounds and covers the literature from 2009 to 2020.     

A Catalytic Enantioselective Synthesis of Biologically Interesting Cyclopropane Amines

The synthesis of cyclopropane amine has attracted considerable interest from organic chemists because of the biologically importance and its occurrence in numerous natural products¹. Several synthetic cyclopropane amines have been used as drugs, e.g. the monoamine oxidase inhibitor tranylcypromine (1)². However, it has been found that two enantiomers of chiral cyclopropane amine have different pharmacological effects³,which demands organic chemists to develop efficient methods to prepare them enantioselectively. Previous synthesis of enantiomerically pure cyclopropane amines involves resolution of racemic cyclopropane carboxylic acid followed by Curtius degradation⁴.     

Constructing molecular complexity and diversity: total synthesis of natural products of biological and medicinal importance

The advent of organic synthesis and the understanding of the molecule as they occurred in the nineteenth century and were refined in the twentieth century constitute two of the most profound scientific developments of all time. These discoveries set in motion a revolution that shaped the landscape of the molecular sciences and changed the world. Organic synthesis played a major role in this revolution through its ability to construct the molecules of the living world and others like them whose primary element is carbon. Although the early beginnings of organic synthesis came about serendipitously, organic chemists quickly recognized its potential and moved decisively to advance and exploit it in myriad ways for the benefit of mankind. Indeed, from the early days of the synthesis of urea and the construction of the first carbon-carbon bond, the art of organic synthesis improved to impressively high levels of sophistication. Through its practice, today chemists can synthesize organic molecules--natural and designed--of all types of structural motifs and for all intents and purposes. The endeavor of constructing natural products--the organic molecules of nature--is justly called both a creative art and an exact science. Often called simply total synthesis, the replication of nature's molecules in the laboratory reflects and symbolizes the state of the art of synthesis in general. In the last few decades a surge in total synthesis endeavors around the world led to a remarkable collection of achievements that covers a wide ranging landscape of molecular complexity and diversity. In this article, we present highlights of some of our contributions in the field of total synthesis of natural products of biological and medicinal importance. For perspective, we also provide a listing of selected examples of additional natural products synthesized in other laboratories around the world over the last few years.     

Chiral thioether-based catalysts in asymmetric synthesis: recent advances

Chiral, non-racemic, thioethers have provided organic chemists with useful tools for developing new reagents and catalysts for practical modern asymmetric synthesis. Disclosed herein is a brief personal overview on major recent contributions in this field in which the sulfur atom plays a leading role in the reaction pathway.     

Preface for the Special Column of Methane Transformation

Methane is the main constituent of natural gas, coal-bed gas, landfill gas and methane hydrate resources. These resources may be used more efficiently as clean fuels or as chemical feedstocks if methane can be effectively transformed into liquid fuels or chemicals. However, methane only possesses C-H bonds and is a very stable organic molecule hard to functionalize. The C-H activation, particularly the selective functionalization of C-H bonds in saturated hydrocarbons, remains a difficult challenge in chemistry. The present technology for chemical utilization of methane involves the steam reforming of methane to synthesis gas and the subsequent transformation of synthesis gas to methanol or hydrocarbon fuels via methanol synthesis or Fischer-Tropsch synthesis. However, the steam reforming of methane is a high-cost process. The development of more efficient and economical processes for methane transformation is a dream of all chemists and chemical engineers. I think that this is also one of the most important themes of the Journal of Natural Gas Chemistry.