matter is composed of a large number of molecules, atoms or ions that cannot be seen by humans. Synthetic chemistry is one of the most powerful tools and means to create new matter. Chemists have used this tool to cleverly create tens of millions of new matters that did not exist in nature through the combination of various elements, promoting the progress and development of human civilization. In addition to the different components of different substances, there may also be differences in three-dimensional space, especially in the micro three-dimensional space at the molecular level or nanoscale. There is a type of matter that has two stereospatial structures (called "enantiomers", referred to as enantiomers), which look exactly the same as the left and right hands of a human, but cannot overlap. This type of matter is called "chiral material" (chiral material or chiral substance). Chiral substances can be composed of chiral molecules or achiral molecules.
Chiral matter is widely present in nature and is closely related to our lives. During the long process of life formation and evolution, chiral matter often has only one configuration that is favored. For example, sugars in nature are all in D configuration, amino acids are all in L configuration, and the double helix structure of DNA is all right-handed helix. Because of this, since the birth of human beings, chiral matter has been integrated into our lives and lives and affecting our health. Most of the drugs we use today are chiral drugs. In addition, chiral materials have also been widely used. For example, chiral liquid crystal materials provide us with a clearer viewing screen; chiral sensing materials, chiral bionic materials, etc. have brought us many longings.
Research on the creation and transformation of chiral substances, as well as the characterization and properties of chiral substances, has formed an emerging chemistry discipline - chiral substance chemistry (also known as "chiral chemistry"). Chiral substance chemistry often uses chiral raw materials, chiral catalysts, etc., or synthesizes and constructs chiral substances through asymmetric reactions, asymmetric catalytic reactions and chiral resolution.
In the chemistry of chiral substances, the synthesis and construction of chiral substances refer to obtaining a single enantiomer or an excess of an enantiomer with optically active chiral substances. It can be seen from this that in addition to focusing on the synthesis efficiency and selectivity (chemical selectivity, regioselectivity, stereoselectivity, etc.) that traditional synthetic chemistry focuses on, the synthesis and construction of chiral substances pay more attention to obtaining products of a single enantiomer. Therefore, it is more difficult to create chiral matter. In order to avoid the generation of "ineffective" enantiomers, the synthesis and construction of chiral substances pursue more precision and environmental friendliness, which represents the future development trend of synthetic chemistry.
After more than 100 years of unremitting efforts, chemists have gradually understood the laws of chiral substance creation. From asymmetric synthesis using chiral sources to enzyme-catalyzed asymmetric synthesis, from asymmetric synthesis of chiral organometallic catalytic to asymmetric synthesis of chiral organic small molecules, chemists have developed many chiral reagents, chiral catalysts, new reactions and new methods for asymmetric synthesis, and have created many chiral substances, including chiral drugs, chiral pesticides, chiral liquid crystal materials, etc., which has greatly promoted the development of chiral substance chemistry. At present, chiral substance chemistry has been deeply intertwined with life sciences, environmental science, information science, materials science, space science, etc., and will play an increasingly important role in understanding nature, interpreting the origin of life, protecting human health, and protecting the environment. The properties of chiral substances and the enantiomers of chiral substances used in
chiral substances are exactly the same in composition, and the physical and chemical properties are also exactly the same in an achiral environment, such as having the same melting point, boiling point, density, chemical reaction, solubility, spectral properties, etc. However, in a chiral environment, there are great differences in some physical and chemical properties between the enantiomers, such as having opposite optical rotations, different odors, etc. Since the basic substances that make up living organisms (such as proteins, DNA, sugar, etc.) are optically pure chiral substances, living organisms themselves are a chiral environment. Therefore, it is not surprising that the enantiomers of chiral drugs exhibit different physiological activities in life.
Chiral drugs are an important discovery of human beings in the 21st century. In ancient times, in order to survive, people learned from their life experience that certain natural substances could cure diseases and pain and became the origin of medicine. For example, the "Shennong Bencao Jing" in my country around the 1st century AD and the "Compendium of Materia Medica" by Li Shizhen of the Ming Dynasty are the masterpieces. At that time, humans had already used natural chiral compounds to treat diseases without realizing it, such as using quinine, Artemisia annua, etc. to treat malaria. In the 1930s, the advent of sulfonamide drugs opened a new era of chemotherapy. Subsequently, many drugs were synthesized and saved countless lives. But at that time, people lacked the understanding of chiral drugs, and did not know that the enantiomers of chiral drug molecules may have different pharmacological effects, which ultimately led to the occurrence of the "reaction stop" event. In the 1950s, "reaction stop" (thalidomide, thalidomide) was used as a sedative drug to alleviate the early morning vomiting reaction of pregnant women, resulting in 12,000 fetal malformations. Later studies found that thalidomide in R configuration has a sedative effect, while thalidomide in S configuration without sedative effect is the culprit for teratogenicity. Since then, chiral drugs have been highly valued. Taking the Pharmacopoeia of the People's Republic of China (2010 edition) as an example, there are about 440 chiral drugs, of which 319 have clear chiral configuration requirements, accounting for 72.5% of all chiral drugs. Among the top 20 best-selling drugs in the world in 2019, chiral drugs account for 14. More than 2/3 of the drugs currently under development are chiral drugs.
Pesticides are essential for protecting crops and increasing grain yields. Among commercial pesticides, more than 25% are chiral pesticides, but in the past, most of these chiral pesticides were sold in racemate form. Like chiral drugs, chiral pesticides often have only one configuration that is effective, and their enantiomers are not only ineffective, but sometimes even harmful to the environment. Therefore, since the 1990s, the development of single-configured chiral pesticides has become increasingly common. The use of single-configured chiral pesticides not only protects plants, increases grain yield, but also saves resources and reduces the harm of ineffective isomers to the environment. As for chiral herbicides, the Netherlands and Switzerland no longer allow chiral phenoxycarboxylic acid racemic mixture registration; some countries have also announced a reduction in pesticide usage, such as the Netherlands, Sweden and Denmark have announced a 50% reduction in pesticide usage within 10 years. This forces pesticide companies to produce single enantiomers in chiral pesticide production. Therefore, pesticide companies at home and abroad are currently promoting single enantiomer chiral pesticides. This undoubtedly plays a positive role in promoting environmental protection and sustainable development.
Although the research on chiral materials started early compared with chiral substances such as chiral drugs and chiral pesticides, due to the relatively complex structure of chiral materials, our understanding and mastery of their properties is still extremely limited. In addition to having a deeper understanding of the chiral helical structure and its physiological functions of proteins, as well as the liquid crystal properties of chiral liquid crystal materials, the potential properties of many other chiral materials still need to be explored and discovered. Chiral materials have played an increasingly important role in our daily life and even in national defense construction. The most prominent of them are chiral liquid crystal materials, especially blue-phase liquid crystal materials. Blue-phase liquid crystal materials are mainly composed of compounds or mixtures composed of strongly twisted chiral molecules. They are sensitive to external stimuli and have an ideal display material in the microsecond range. They have important application prospects in optical computers and laser shielding. In addition, scientists have also created chiral materials such as chiral conductive polymer materials, chiral mesoporous materials, chiral nanomaterials, etc. through chiral doping. Some chiral materials have shown good application prospects in information storage and processing, wave absorption, sensing, etc.
Development trends and prospects of chiral substance chemistry
has gone through cross-century exploration and development, and chiral substance chemistry research has entered a new stage of development. Human beings have been able to achieve the precise creation of chiral substances through artificially synthesized chiral catalysts. The chiral drugs, chiral pesticides, chiral liquid crystal materials and other created have benefited human society.The 2001 Nobel Prize in Chemistry was awarded to three scientists who have made outstanding contributions to the creation of chiral substances, which is a recognition of the development achievements in this field. Now, the research objects of chiral substance chemistry have expanded from the small molecule level to the macromolecular and supramolecular levels. Research on the performance of chiral substances in has received more attention, and chiral substances have shown good application prospects in liquid crystal display, biosensing, information storage, etc. Creating chiral substances more accurately, efficiently and sustainably, studying the application of chiral substances in disciplines such as life sciences, environmental science, information science, materials science, space science, and exploring efficient detection methods and analytical methods of chiral substances are becoming the forefront and hot spots in the chemistry research of chiral substances.
Creating chiral substances more accurately has become the development trend of the discipline of chiral substance chemistry. After more than a century, especially in recent decades, there have been many ways to create chiral matter. Now, almost any single enantiomer of chiral compounds can be synthesized, and the synthesis of some chiral compounds is not only accurate, but also efficient, and has been practically used in industrial production. However, such precise reactions and methods are still very limited. Although the single enantiomers of many chiral compounds can be synthesized, their efficiency is still very low and have no practical application value. Many chiral drugs are still produced by chiral separation rather than asymmetric catalytic methods; many chiral pesticides are still produced in racemate form. The construction of chiral materials is still in the early stages of research, and it is still far from achieving precise creation. In short, whether it is the synthesis of chiral molecules such as chiral drugs and chiral pesticides, or the assembly and construction of chiral materials, they all require precision, and social sustainable development also requires precision in material creation. Nobel Prize winner in chemistry Noyori proposed in 2001: "The future synthetic chemistry must be economical, safe, environmentally friendly, and resource-saving chemistry. Chemists need to work hard to achieve 'perfect reaction chemistry', that is, with 100% selectivity and 100% yield, only the required products are generated without waste." Therefore, focuses on the development of more efficient and highly selective chiral reagents and catalysts, asymmetric synthesis of new reactions, new methods, new concepts and new strategies, and realizing the precise creation of chiral substances is an inevitable trend in the development of the discipline of chiral substance chemistry.
The discipline of chiral substance chemistry started late in my country, but with the strong support of the National Natural Science Foundation of China, the Ministry of Science and Technology, the Ministry of Education, the Chinese Academy of Sciences and other departments, after more than 30 years of unremitting efforts by Chinese scientists, it has made great progress and has reached or been at the world's advanced level in some research directions. For example, in the design and synthesis of chiral ligands and catalysts, chiral substances have produced internationally influential research results in creating new reactions, new methods, new strategies, new concepts, etc. However, compared with the United States, Japan and other countries, my country still has a big gap in the overall research level of chiral substance chemistry. Its main manifestations are: ① There are not enough landmark and visible research results produced by my country's chiral substance chemistry research; ② There are many scientists engaged in chiral substance chemistry research in my country, but there are few research teams and academic leaders who have truly international influence; ③ my country's chiral substance chemistry research mainly focuses on a few research directions, and the phenomenon of repeated research is relatively serious; ④ my country has few chiral technologies and has not been well applied, and there are very few chiral technologies used by Chinese enterprises. Although the above problems still exist in the discipline of chiral substance chemistry in my country, its development momentum is very good.
Matter is the basis for human progress. Creating new substances is the central task of synthetic chemistry and is also the forefront and focus of competition for international innovation capabilities in the new century. Today's rising information technology, environmental technology, biotechnology, space technology, etc. all rely on "advanced" substances. These "advanced" substances are often something that nature cannot directly give to us and need to be created manually. Developing accurate, efficient, environmentally friendly and sustainable methods and technologies for creating chiral substances is the only way to obtain chiral substances.Therefore, with the strong support of the National Natural Science Foundation of China, the Ministry of Science and Technology, the Ministry of Education, the Chinese Academy of Sciences and other departments, we need to target the major needs of the country, base ourselves on the frontier of the discipline, strengthen the overall layout, focus on the "point" and lead the "surface", and maximize the innovation ability and potential of my country's chiral substance chemistry discipline; work together, adhere to the foundation and the frontier, vigorously promote the intersection and integration of disciplines, strive to solve the key scientific problems in the creation of chiral substances, enrich and develop the basic theories of chiral substance creation, establish and develop core technologies for chiral substance creation, develop advanced chiral substances, and establish new methods for separation and analysis and characterization of chiral substances; strengthen the awareness of green and sustainable substance creation, establish a resource information sharing platform for chiral substance chemistry disciplines, and strive to promote the deep integration of production, education and research, so that chiral substance chemistry can better serve national construction and social and economic development, and make greater contributions to the progress of human society.
This article is excerpted from the introduction part of "China's Discipline Development Strategy·Chiral Material Chemistry" (Edited by the National Natural Science Foundation of China, Chinese Academy of Sciences. Beijing: Science Press, 2020.7). The content has been deleted and the title was added by the editor.
"Chinese Discipline Development Strategy·Chiral Material Chemistry"
ISBN 978-7-03-064301-8
Series Planning: Hou Junlin Niu Ling
Content Introduction
Chiral Material Chemistry is an emerging chemistry discipline that studies the creation, transformation, characterization, performance, etc. of chiral substances. It is deeply intertwined with life sciences, environmental science, information science, materials science, space science, etc., and plays an increasingly important role in understanding nature, interpreting the origin of life, protecting human health, and protecting the environment. This book embodies the wisdom of dozens of chemists in my country, analyzes the discipline status, contributions to society, discipline development level and trends of chiral substance chemistry, and puts forward development suggestions and countermeasures.
"China Discipline Development Strategy·Chiral Material Chemistry" is suitable for high-level strategic and management experts, teachers and students of universities in related fields, and researchers from research institutions. It is an important guide for scientific and technological workers to understand the laws of discipline development and grasp cutting-edge fields and key directions. It is also an important decision-making reference for science and technology management departments. It is also an authoritative reading book for the public to understand the current status and trends of chiral material chemistry.
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Catalog
Total order i
Foreword v
Abstract vii
Abstract xi
Chapter 1 Introduction 1
Section of chiral substance chemistry 1
Section of chiral substance synthesis and construction 2
Section of chiral substance separation analysis and characterization 6
Section of chiral substances 4Properties and applications of chiral substances 8
Section of five Development trends and prospects of chiral substance chemistry chemistry 2
Section of chiral substances 6
Section of fourProperties and applications of chiral substances 8
Section of five Development trends and prospects of chiral substance chemistry chemistry 10
References 13
Section 1 Introduction 17
Section 2 Application of chiral reagents in asymmetric synthesis 19
Section 3 From enzyme catalysis to cell factory 33
Section 4 Transition metal catalytic asymmetric synthesis 49
Section 5 Lewis acid catalytic asymmetric synthesis 66
Section 6 Organic small molecule catalytic asymmetric synthesis 84
Section 7 Photo-promoted asymmetric synthesis 103
Section 8 Absolute asymmetric synthesis and asymmetric autocatalysis 122
Section 9 Asymmetric synthesis of complex natural products and drug molecules 138
Section 10 Summary and Prospect 157
References 159
Chapter 3 Construction of chiral inorganic materials and hybrid materials 205
Section 1 Introduction 205
Section 2 Construction of chiral inorganic materials 207
Section 3 Construction of chiral metal-organic molecular containers 228
Section 4 Synthesis of chiral metal-organic frameworks and chiral covalent organic framework materials 241
Section 5 Outlook 259
References 261
Chapter 4 Synthesis of chiral polymers 272
Section 1 Introduction 272
Section 2 Asymmetric polymerization reaction 285
Section 3 Asymmetric copolymerization 304
Section 4 Regulation of polymer optical activity 312
Section 5 Properties and functions of chiral polymers 332
Section 6 Outlook 351
References 353
Chapter 5 Separation and analysis of chiral substances 372
Section 1 Introduction 372
Section 2 Chromatography 374
Section 3 Capillary electrophoresis 399
Section 4 Chemical resolution 403
Section 5 Biological resolution 409
Section 6 Extraction and resolution method 411
Section 7 Membrane resolution method 412
Section 8 Outlook 414
References 418
Chapter 6 Characterization of chiral matter 425
Section 1 Overview of the basic principles of spectral characterization of chiral matter 425
Section 2 Spectral characterization method 429
Section 3 Nonlinear spectroscopy method of interface supramolecular chirality 440
Section 4 Nuclear magnetic resonance method 449
Section 5 Chiral structure and morphological characterization 454
Section 6 Outlook 462
References 463
Chapter 7 Chiral Drugs 480
Section 1 Introduction 480
Section 2 Chiral Drug Design and Principles 481
Section 3 Stereo-selectivity of Chiral Drug Pharmacy 486
Section 4 Stereo-selectivity of Chiral Drug Toxicology 492
Section 5 Stereo-selectivity of Chiral Drug Metabolites 496
Section 6 Interactions of Chiral Drugs 507
Section 7 Outlook 514
References 516
Chapter 8 Environmental Behavior and Ecological Security of Chiral Pesticides 525
Section 1 Introduction 525
Section 2 Evaluation method of enantiomers of chiral pesticides 526
Section 3 Types and development of chiral pesticides 528
Section 4 Enantioselective environmental process of chiral pesticides 534
Section 5 Enantioselective toxicology of chiral pesticides 541
Section 6 Outlook 545
References 547
Chapter 9 Chiral aggregate materials 555
Section 1 Principles and methods for construction of chiral aggregates 555
Section 2 Supramolecular chiral effects of chiral aggregates 557
Section 3 Functions of chiral aggregates 573
Section 4 Chiral functional materials 595
Section 5 Outlook 604
References 606
Keyword index 6
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