分子识别指导下的有机分子设计、合成和组装——世纪交替时代的有机化学

在21世纪即将来临之际,有机化学将面临生命科学、环境科学和材料科学越来越多的挑战。本文回顾了在分子识别指导下的有机分子的设计、合成和组装这个新领域的诞生和发展,认为这个领域将成为新世纪有机化学发展的一个重要方向。它的发展和应用不仅使得有机化学可能较好地面对新挑战,同时能推动有机合成化学自身的发展。     

Multi-Step Continuous-Flow Organic Synthesis: Opportunities and Challenges

Continuous-flow multi-step synthesis takes the advantages of microchannel flow chemistry and may transform the conventional multi-step organic synthesis by using integrated synthetic systems. To realize the goal, however, innovative chemical methods and techniques are urgently required to meet the significant remaining challenges. In the past few years, by using green reactions, telescoped chemical design, and/or novel in-line separation techniques, major and rapid advancement has been made in this direction. This minireview summarizes the most recent reports (2017–2020) on continuous-flow synthesis of functional molecules. Notably, several complex active pharmaceutical ingredients (APIs) have been prepared by the continuous-flow approach. Key technologies to the successes and remaining challenges are discussed. These results exemplified the feasibility of using modern continuous-flow chemistry for complex synthetic targets, and bode well for the future development of integrated, automated artificial synthetic systems.     

光催化应用于药物合成反应实验教学的设计与改革

可见光诱导的光催化具有绿色、高效、可持续等特点,在有机医药中间体和药物分子的合成上极具创新性.近年来,将前沿性、创新性的科研成果实施于本科实验教学项目中已成为高校实验教学改革的重点与趋势之一.本实验利用苝二酰亚胺作为光催化剂,在温和的光照条件下高效选择性氧化硫醚得到亚砜.通过本实验的学习,为学生实践绿色、低能耗的有机化...     

有机化学知识在高分子材料合成创新实验中的运用——分享几个实例

针对目前教学中存在的理论课程之间、实验课程与理论课程之间关联不够紧密等问题,探索了通过"知识关联"将有机化学基本知识运用到高分子材料合成创新实验中的教学思路。以新试剂合成及应用、荧光聚酯合成、聚酰胺合成、聚酯水解等为例,介绍了如何将有机化学新理论、新方法、新试剂应用于本科高分子化学和高分子材料实验教学,以及如何将有机化学的理论知识和实验手段应用于高分子材料合成教学中。实践表明:通过"知识关联",将有机化学基础理论知识和实验技能应用于高分子合成实验中可以提高学生对所学知识的理解和运用能力,增强学生的实验探索兴趣,有效改进了高分子材料合成实验教学的课堂气氛。     

Synthetic Strategies for Constructing Two‐Dimensional Metal‐Organic Layers (MOLs): A Tutorial Review

Two‐dimensional (2D) metal‐organic layers (MOLs) are the 2D version of metal‐organic frameworks (MOFs) with nanometer thickness in one dimension. MOLs are also known as 2D‐MOFs, 2D coordination polymers, ultrathin MOF nanosheets (UMOFNs) or coordination nanosheets in literature. This new category of 2D materials has attracted a lot of interests because of the opportunity in combining molecular chemistry, surface/interface chemistry and material chemistry of low dimensional materials in these systems. Several synthetic strategies have been developed for the construction of 2D MOLs, but the general synthesis of MOLs still presents a challenge. This tutorial level review summarizes the recent progress in the fabrication of novel 2D MOLs and aims to highlight challenges in this field.     

Synthesis and Supramolecular Functional Assemblies of Ratiometric pH Probes

Tracking pH with spatiotemporal resolution is a critical challenge for synthetic chemistry, chemical biology and beyond. Over the last decade, different small probes and supramolecular systems have emerged for in cellulo or in vivo pH tracking. However, pH reporting still presents critical limitations, such as background reduction, improved sensor stability, cell targeting, endosomal escape, near- and far-infrared ratiometric pH tracking and adaption to new imaging techniques (i.e., super-resolution). These challenges will require the combined efforts of synthetic and supramolecular chemistry working together to develop the next generation of smart materials that will resolve current limitations. Herein, recent advances in the synthesis of small fluorescent probes, together with new supramolecular functional systems employed for pH tracking, are described with an emphasis on ratiometric probes. The combination of organic synthesis and stimuli-responsive supramolecular functional materials will be essential to solve future challenges of pH tracking, such as improved signal to noise ratio, on target activation and microenvironment reporting.     

可见光促进的偕二氟烯烃制备与应用研究进展

偕二氟烯烃化合物在医药、材料、精细化工等领域具有广泛的应用,同时也是一类非常重要的用于制备各类复杂的有机氟化合物的有机合成中间体.可见光催化反应具有条件温和、绿色清洁等特点,已经成为有机化学中非常重要的合成手段之一.本文综述了近年来可见光促进的偕二氟烯烃化合物的制备及其在有机合成化学中的应用.     

有机合成化学"三位一体"混合教学模式探索与实践

In order to improve the quality of teaching and cultivate chemical innovation talents in university for nationalities, in the course of organic synthetic chemistry curriculum construction, efforts were made to overcome problems such as the single teaching objective, abstract and boring teaching content, tedious and relatively dull teaching methods and low enthusiasm for students' learning, etc. According to the study rule of "before class-on class-after class", the trinity mixed teaching mode of "teaching goal-teaching means-practice examination" was constructed. Through the construction of the "teaching goal-teaching means-innovative practice" trinity mixed teaching mode, we refined teaching objectives, optimized teaching methods, implemented small classes, improved assessment methods, designed comprehensive laboratory programs, reinforced practices, and reformed the assessment measures. Discussion on teaching reform and practice of organic synthetic chemistry was carried out from multiple perspectives. Through the practice of teaching reform, the teaching effect has been improved, the enthusiasm of students to learn organic synthetic chemistry has been improved, and the expected effect of cultivating students' innovative ability has been achieved.     

Design and Synthesis of Carbon Nanotube Segments

The selective and predictable synthesis of structurally uniform carbon nanotubes (CNTs) represents a long‐standing goal in both nanocarbon science and synthetic organic chemistry. This Review focuses on synthetic studies toward the controlled synthesis of CNTs with single chirality through the organic synthesis of CNT segments and the organic template assisted growth of CNTs.     

Toward an RNaseA mimic: A DNAzyme with imidazoles and cationic amines

Site-specific RNA cleavage has received considerable attention over the years. Directed synthesis to append imidazoles or amines or both to oligonucleotides to target specific RNA cleavage represents an exciting avenue of research. However, to date catalysis by such synthetic constructs, particularly in terms of turnover, has been difficult to observe. This is the first report of a truly catalytic M2+-independent DNAzyme synthetically modified with imidazoles and cationic amines that would seem to mimic RNaseA. This work now demonstrates how synthetic organic chemistry, when merged with combinatorial selection, can result in a new class of DNAzymes that meets the ongoing synthetic challenges for developing relatively small biomimetic catalysts.     

Solid-phase synthesis of heterocyclic aromates: applicability towards combinatorial chemistry; a review

Because of their biological activity, stability in vivo, the rigid spatial positioning of their substituents, and their synthetic challenges, heterocyclic aromates continue to be of interest to both academic and industrial medicinal chemists. Currently, many drug-like heterocyclic aromates are prepared via solid-phase organic chemistry methods. This review examines the applicability of those methods towards combinatorial chemistry with respect to the basic demands of such an approach: 1) synthesis, work-up and subsequent purification should be easily automated enabling the efficient simultaneous synthesis of large numbers of highly pure compounds in a minimum amount of time, 2) large diversity among the ligands to be synthesized, 3) high conversion rates of the individual reaction steps, and 4) the use of commercially available starting materials. Although many methods have been developed for the synthesis of heterocyclic aromates, very few of the available methods enable the synthesis of highly diverse heteroaromatic libraries.     

Enzymes as Catalysts in Synthetic Organic Chemistry [New Synthetic Methods (53)]

Enzymes have great potential as catalysts for use in synthetic organic chemistry. Applications of enzymes in synthesis have so far been limited to a relatively small number of largescale hydrolytic processes used in industry, and to a large number of small-scale syntheses of materials used in analytical procedures and in research. Changes in the technology for production of enzymes (in part attributable to improved methods from classical microbiology, and in part to the promise of genetic engineering) and for their stabilization and manipulation now make these catalysts practical for wider use in large-scale synthetic organic chemistry. This paper reviews the status of the rapidly developing field of enzyme-catalyzed organic synthesis, and outlines both present opportunities and probable future developments in this field.     

Strategies for Synthesis of Imidazo[1,2‐a]pyridine Derivatives: Carbene Transformations or C−H Functionalizations

The imidazo[1,2‐a]pyridines are an important target in organic synthetic chemistry and have attracted critical attention of chemists mainly due to the discovery of the interesting properties exhibited by a great number of imidazo[1,2‐a]pyridine derivatives. Although lots of synthetic methods of imidazo[1,2‐a]pyridines have been developed in the past years, the chemistry community faces continuing challenges to use green reagents, maximize atom economy and enrich the functional group diversity of product. Undoubtedly, with its low cost and lack of environmentally hazardous byproducts, cascade reactions and C?H functionalizations are ideal strategies for this field. In this record we highlight some of our progress toward the goal to synthesis of imidazo[1,2‐a]pyridine derivatives through carbene transformations or C?H functionalizations.     

Heteroarene-tethered Functionalized Alkyne Metamorphosis

Heteroarene-tethered functionalized alkynes are multipotent synthons in organic chemistry. This detailed Review described herein offers a thorough discussion of the metamorphosis of heteroarene-tethered functionalized alkynes, an area which has earned much attention over the past decade in the straightforward synthesis of architecturally complex heterocyclic scaffolds in atom and step economic manner. Depending upon the variety of functionalized alkynes, this Review is divided into multiple sections. Amongst the vast array of synthetic transformations covered, dearomatizing spirocyclizations and cascade spirocyclization/rearrangement are of great interest. Synthetic transformations involving the heteroarene-tethered functionalized alkynes with scope, challenges, limitations, mechanism, their application in the total synthesis of natural products and future perceptions are surveyed.     

Organoselenium Chemistry in Stereoselective Reactions

Selenium-based methods have developed rapidly over the past few years asnd organoselenium chemistry has become a very useful tool in the hands of synthetic chemists. The different reactivity of selenium-containing compounds in contrast to the sulfur analogues has led to versatile and new synthetic methods in organic chemistry. Various functionalities can be selectively introduced into complex molecules under very mild reaction conditions. In this review, the principles of organoselenium chemistry are traced back to their origins and are highlighted with respect to stereoselective synthesis. The unique properties of selenium allow the development of new and highly selective transformations, which can be employed subsequently in new routes for the synthesis of versatile chiral building blocks and for natural product synthesis.     

Carbohydrate-derived porous carbon materials: An ideal platform for green organic synthesis

Porous carbon materials have attracted much attention in the field of organic synthesis in recent years,due to their tunable properties, excellent catalytic activity and stability. Biomass-based carbohydrates emerge as an ideal precursor for the generation of these materials owing to their renewability, low cost,non-toxicity and high content of functional groups. Thus, carbon materials prepared from carbohydrates is of considerable importance for the sustainable development of organic chemistry....     

现代有机合成的新概念及研究进展

概念是有机合成化学发展的基础之一,新概念的产生和发展可为有机合成开拓新的研究领域和发展方向。此文介绍现代有机合成中的一些新概念和新方法,结合具体的有机合成反应实例展示有机合成在这些概念的基础上取得的新成果和新进展,并综合归纳了现代有机合成的发展方向和应重视的研究领域。     

α-羟基取代膦酸酯类化合物的合成研究进展

含磷化合物一直是有机化学研究的热点之一,许多合成药物以及天然产物都含有磷原子。其中,α-羟基取代膦酸酯类化合物是重要的有机合成中间体,其在有机合成中的应用一直受到广泛关注。文章详细综述了α-羟基取代膦酸酯类化合物的合成方法。     

The Symbiotic Relationship Between Drug Discovery and Organic Chemistry

All pharmaceutical products contain organic molecules; the source may be a natural product or a fully synthetic molecule, or a combination of both. Thus, it follows that organic chemistry underpins both existing and upcoming pharmaceutical products. The reverse relationship has also affected organic synthesis, changing its landscape towards increasingly complex targets. This Review article sets out to give a concise appraisal of this symbiotic relationship between organic chemistry and drug discovery, along with a discussion of the design concepts and highlighting key milestones along the journey. In particular, criteria for a high-quality compound library design enabling efficient virtual navigation of chemical space, as well as rise and fall of concepts for its synthetic exploration (such as combinatorial chemistry; diversity-, biology-, lead-, or fragment-oriented syntheses; and DNA-encoded libraries) are critically surveyed.