1.Исследовано поверхностное натяжение несколъких чистых алифатичдских аминов при 20 ℃ методом наиболъщего давления пузыовковм(метод П.А.Ребиндера).

Aqueous zinc ion batteries (AZIBs) as an emerging battery energy storage technology have attracted widespread attention and developed rapidly in recent years due to the merits of high safety, low price, high energy density, environmental friendliness, easy manufacturing, etc., showing good application value and prospect in large-scale energy storage and other fields. Embarking from the current scientific issues existed in AZIBs, we review the important progress in cathode and anode materials and electrolyte used in AZIBs in this article. Firstly, the characteristics of multiple cathode materials that developed and their electrochemical reaction mechanism are analyzed and summarized. Afterward, the challenge and improving strategy for metal zinc anode are discussed, and the features of different aqueous electrolytes and the optimization solution are analyzed. Finally, the scientific problems to solve and technical challenges for the practical application in the future of this novel battery technology are summarized and prospected.

The concept of the molecular orbital composition is often involved in quantum chemistry literatures. However, no enough emphasis has been placed on the corresponding calculation methods, and even there exist some serious misunderstandings. In this article, the basic concepts and calculation methods of composition of basis functions, atomic orbitals and atoms in molecular orbitals are discussed in detail, the differences between various methods are analyzed and compared with examples, meanwhile, the problems in calculations and analyses that need to be noticed are pointed out, the suggestions for choosing appropriate calculation methods are also given.

Hantzsch Esters were first synthesized by Arthur Rudolf Hantzsch in 1881, and widely used in pharmaceutical chemistry. The application of Hantsch Esters in organic synthesis in the early time was mainly focused on the dehydrogenation of 1,4-dihydrogen pyridines (DHPs) in the synthesis of functional pyridines. In 1955, Mauzerall and Westheimer found that Malachite Green could be reduced by Hantzsch Esters to generate the hydrogenated product. Then these DHPs were extensively used as a reductant for decades due to their electron and hydrogen donating properties. In recent years, scientist found that C—C bond cleavage at 4-position of 4-substituted Hantzsch Esters would lead alkyl transfer, and the alkylation process was a radical process. With the rapid development of free radical chemistry, various alkylation reactions using 4-substituted Hantzsch Esters as alkylation reagent have been developed, such as addition reactions of imines and alkenes; cross-coupling reactions with aryl halides; substitution reactions with functional aromatics; Tsuji-Trost reaction; radical insertion with sulfur dioxide; and asymmetric alkylation etc. The advantages in alkylation transfer by using 4-substituted Hantzsch Esters as alkyl source in the past five years were witnessed dramatically: (1) Highly toxic alkyl metal reagents could be avoided in the alkylation reactions; (2) Compared with the moisture sensitivity of alkyl metal reagents Hantzsch Esters are easily handling; (3) 1,4-Dihydrogen pyridines (DHPs) are biologically-inspired model molecular of reduced nicotinamide adenine dinucleotide (NADH), which would expand the application in biosynthesis. A brief summary in this field is presented in this review, and the advances are classified according to different reaction types. Although these creativity works were developed, there are still some challenges: (1) Could aromatic groups at 4-position of 4-substituted Hantzsch Esters serve as arylation reagents? (2) How to recover the rest pyridine part of Hantzsch Esters after alkylation; (3) New type reactions need to be developed for the asymmetric synthesis.

During the past several decades, Suzuki-Miyaura cross-coupling reaction has emerged and flourished as one of the most remarkable and practical methods to construct C—C bond. The substrates, organoboronic compounds, are usually more stable, less toxic and easier to obtain compared with other metal or metalloid alternatives. Suzuki-Miyaura cross-coupling reaction possesses extraordinary merits of demonstrated efficiency, broad functional group compatibility and mild reaction conditions. It has been the premier method to construct C—C bond for organic synthetic chemists and has been widely applied in the industrial syntheses. The rapid development of Suzuki-Miyaura cross-coupling reaction is accompanied with the progress of mechanism studies. It is well accepted that the catalytic cycle of Suzuki-Miyaura cross-coupling reaction contains three main steps: oxidative addition of organic halides to Pd catalysts, transmetalation between oxidative addition intermediates and organoboronic compounds, and reductive elimination from transmetalation intermediates to form C—C bond along with regenerating Pd catalysts. However, these three main steps can be influenced by diverse reaction conditions, and different reaction pathways may occur within each single step. Furthermore, beyond the oxidative addition and transmetalation intermediates, other transient but crucial intermediates may exist. To figure out these issues and discover more insights into Suzuki- Miyaura cross-coupling reaction, numerous researchers have designed and conducted systematic investigations. Herein, the recent progress of mechanism studies is summarized and discussed. The steps of oxidative addition, transmetalation and reductive elimination are discussed in detail. Moreover, a brief introduction of transition-metal-free and base-free Suzuki- Miyaura cross-coupling reactions which show more possibilities of the reaction mechanism is given. Besides summary of precedent research works, our opinions about future development of the mechanism studies are also given. Although breakthroughs have been made in the mechanism studies, further investigations are needed to bring comprehensive knowledge of this reaction and help us further optimize the reaction conditions.

The C=C double bond cleavage of NH₂-functionalized enaminones has been realized at room temperature to provide various N-sulfonyl amidines by reacting with sulfonyl azides. The reactions take place with good substrate tolerance in the presence of 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) without any metal or oxidant reagent. The ¹⁵N-labelling experiment on enaminone indicates that the sulfonyl azide component donates solely the sulfonamide fragment, and the reaction mechanism involving a key decomposition of the in situ generated 1,2,3-triazoline intermediate is convictively supported.

Click chemistry has attracted great interests due to a wide variety of superior merits, including a wide range of applications, simplified experimental condition, rapid reaction speed, higher functional group conversion, environmental friendly and selectivity. And conception of click chemistry contributed to the synthetic chemistry apparently, in particular, with respect to pharmaceutical manufacture and biomedical materials, resulting in the most useful and promising synthetic method. Furthermore, thiol-ene/yne click chemistry, utilizing inclusion of visible light or UV light as catalytic medium, is a comparatively novel kind of click chemistry in comparison to several types of conventional reactions. In addition, the properties of the creative reaction stems from the combination the photoinitiated chemical reaction with the forementioned traditional click chemistry, providing a flexible approach to occur reaction within the oriented region and functional group. This review highlights the recent research on the preparation of functional polymeric microsphere, amphipathic block well-defined polymer, materials employed in the molecular device, desired dendritic polymers and chemistry modification via thiol-ene/yne click chemistry. Moreover, the problems and solutions are given for the future development of thiol-ene/yne click chemistry.

Hydrogen-bonded organic frameworks (HOFs), usually self-assembled by organic or metal-organic building blocks via intermolecular H-bonding interactions, have become a unique type of crystalline porous material. Although the weak and flexible nature of hydrogen bonds makes most HOFs fragile, the high stability and permanent porosity could be realized by the judicious selection of rigid building blocks with special spatial configuration as well as the introduction of framework interpenetration and/or other intermolecular interactions like π-π stacking and electrostatic interactions, etc. Compared with other crystalline porous materials like metal-organic frameworks (MOFs) and covalent-organic frameworks (COFs), HOFs feature mild preparation condition, high crystallinity, permissible solution processability, easy healing and regeneration, etc. These distinguishing merits make HOFs capable to be used as unique multifunctional porous materials. Herein, we first review the basic rules to design and synthesize stable and porous HOFs, and then systematically summarize the representative supramolecular synthons and backbones that have been used to build stable and porous HOFs. Emphasis is put on the potential applications of HOFs in gas adsorption and separation, proton conduction, heterogeneous catalysis, luminescence and sensing, biological applications, enantiomeric resolution and aromatic compounds separation, pollutants removal, and structure determination, etc.

Vacuum liquid chromatog. was used to sep. >10 but <20 kinds of terpenes in Anemonia sulcata in the sea near Okinawa, Japan. The sample was extracted with acetone and concentrated followed by extration with n-hexane and the extract was dissolved in n-hexane-ethyl acetate (8:2 vol./vol.) and placed on Merek silica gel H 60. Gradient elutions were carried out using n-hexane 100%, n-hexane-Et acetate (95:5, 9:1, 8:2, and 6:4 vol./vol.) and finally Et acetate 100%. Each fraction was 200 mL and 10 fractions were collected. Total time spent was 2 h. Advantages and disadvantages of this method are described.5

Oxidation reactions play important roles in organic synthesis, where hydrogen peroxide and peroxy acids are always employed as oxidants. Urea-hydrogen peroxide (UHP) is recently utilized in numerous oxidation reactions as environment- friendly solidified hydrogen peroxide, due to its advantages such as stable at room temperature, high hydrogen peroxide content (36.2%) and the potential for releasing it in a controlled manner. Several applications of UHP to organic synthesis are summarized according to reaction type, especially for epoxidation, Baeyer-Villiger oxidation, N-oxidation, oxidation of sulfides to sulfoxides and sulfones, oxidative-halogenation and so on.

Nitrile-containing compounds comprise a substantial proportion in the therapeutic drugs. It is an important strategy to introduce nitrile substitute in the small molecule for structure-based medicinal chemistry. The application of nitrile in drug design is reviewed. The nitrile can modulate the physicochemical and pharmacokinetic properties to improve bioavailability, enhance the selectivities and binding affinity to target proteins by hydrogen bond interactions, covalent interactions, polar interactions, and π-π interactions. Meanwhile, the nitrile acts as bioisostere of various functional groups such as carbonyl and halogen groups. In addition, introducing the nitrile to drug molecules can block metabolically labile sites to increase the metabolic stability of drugs.

Many biologically active compounds contain the CF₃ groups as the essential motif. As a result, much attention has been paid to the development of new synthetic methods for the introduction of the CF₃ groups into diverse organic compounds. This review takes a critical look at recent advances of trifluoromethyltion reactions.

Organic solar cells (OSCs) have attracted an extensive attention due to their light-weight, low cost and flexible features. Exploitation of novel polymeric donating materials is one of the mainstreams in the field. To date, a variety of conjugated polymers with excellent electron-donating properties have been developed. Based on these materials, power conversion efficiency of OSCs has reached to 9%. This review classifies these materials based on the chemical structures of the repeating units, and summarizes their progress accordingly. A number of representative materials, which have received much attention, are highlighted from the aspects of designing strategy, properties, device fabrication and performance. It is anticipated to penetrate more deeply the basic relationships among the chemical structure-packing structure-property, which could provide valuable information for the future materials exploitation.

Sulfoximines are a very important class of heteroatom substitutional compounds and have attracted considerable interest. This review deals with methods for the synthesis of sulfoximines and their applications in catalytical asymmetric synthesis, bioactive small molecules synthesis and total synthesis of natural products. The developing trend and prospects for future application of sulfoximines compound are discussed.

Proton-coupled electron transfer (PCET) reactions are a kind of unconventional redox reactions, which exhibit special reactivities and selectivities due to their unique interdependent electron-proton transfer mechanisms. There are three possible pathways of PCET processes, including stepwise electron transfer followed by proton transfer (ETPT), proton transfer followed by electron transfer (PTET), and concerted pathway in which electron and proton transfer synchronously (CEPT), avoiding intermediates with high energy. These reactions have been playing a key role in numerous areas in organic chemistry, inorganic chemistry, bioorganic chemistry, organometallic and material chemistry, including the redox processes in natural and artificial systems, such as the activation for small molecules. Recently, the application of PCET reactions in organic synthesis has received a great deal of attentions and interests. Being accompanied by the development of electrochemical methods and photocatalysts, more and more novel reactions in electrochemistry and photochemistry involve PCET processes have been reported. Applying these electrochemical and photochemical methods, the activation of X—H bond has been achieved via PCET processes, including C—H bond, N—H bond, P—H bond, S—H bond or O—H bond. Thus, based on these crucial processes, a number of vital structures and fundamental frameworks can be synthesized, and various synthetic building blocks and natural products have been attained. For example, pharmaceutical building blocks like 2°-piperidines can be cyanated at their α-position; substituted dimeric pyrroloindolines such as (–)-calycanthidine, (–)-chimonanthine, and (–)-psychotriasine have also been successfully synthesized via PCET mechanism. Moreover, not only the products of reduction of multiple bonds (C=Y bond such as C=C bond, C=N bond and C=O bond), but also the products of self/cross-coupling have been achieved via PCET mechanism. In this review, the recent applications and developments of PCET mechanism in organic synthesis are summarized, including new catalyst systems and new reagents, especially with electrochemical and photochemical methodologies. The future of this area has also been demonstrated from both experimental and theoretical aspects.

Luminescence of conventional fluorophores often becomes weakened or quenched at high concentration or solid state. In contrast, some are non-luminescent in solution but highly emissive in the aggregate or solid state, so called “aggregation-induced emission (AIE)”, which might be resulted from the restriction of intramolecular rotation (RIR) and changes in aggregate morphology. Herein, the latest progress on AIE since 2008 is reviewed, such as: (i) developing chemo-or bio-sensors for detecting ions, gas, small molecules, explosives, proteins, enzymes and so on; (ii) incorporating the AIE unit to realize highly luminescent solid emitters, especially for OLEDs (organic light-emitting diodes); (iii) tuning the aggregation morphology to construct reversible multi-responsive materials stimulated by pressure, heat or solvent vapor; (iv) due to the biocompatibility of aggregate nanoparticles, developing hybrid materials including fluorescent silica nanoparticles, polymeric micelles and electrolytes for applications in cell imaging, structure analysis and bioassay.

Recently visible light photoredox catalysis was widely used in organic synthesis. Due to its low cost, easy availability and environmental friendliness, it has become one of the fastest growing fields in organic chemistry. This review summarizes recent development and application of visible light photoredox catalysis in organic synthesis and also gave its outlook in the future.

The very recent progress in Sonogashira reactions is summarized, which includes the optimization of the reaction conditions, tandem Sonogashira reactions, green Sonogashira reactions, and non-Pd Sonogashira reactions. The mechanistic studies on Sonogashira reactions are also surveyed.

Scientific workers have put the emphasis on the chiral material for a long time, especially in drugs and application of organisms. Chiral metal-organic framework materials (MOFs) have attracted significant attention because of not only their enormous variety of interesting structural topologies but also their wide potential applications. In this paper, its synthesis and application are introduced.

A review with 89 refs. including the distinction between inner- and outer-sphere mechanisms.n

Reductive Heck reaction is a coupling reaction which unsaturated halides react with olefinic compounds at the similar Heck conditions to form the addition products. In this paper, the progress in Heck coupling reaction including catalytic systems, mechanism, applications and limitation in organic chemistry is reviewed.

In recent years, bulk heterojunction solar cells based on small organic molecules are received wide attention due to their simple preparation technique, low-cost, light weight and flexibility. The ideal donor material of organic small molecule is the basis for improving the power conversion efficiency of the organic solar cell. In this review, the research advances of solution processable small molecule donor materials are reviewed systematically, and the development tendency and prospects for future application are discussed.

The supramolecular material has been widely used as a type of drug/gene delivery, molecule device, molecule sensor and catalysis. Due to their excellent biologic and optical properties, cyclodextrins have recently attracted increasingly more attention. In this review the newest development of the supramolecular self-assembly based on cyclodextrin is summarized. The article provided detail information about the synthesis and applications of both of rotaxanes formed by cyclodextrin ring and polymer axes, and supramolecular polymer without polymer backbone.

Aqueous sodium-ion batteries recently have been widely and deeply studied in the energy field due to their prominent advantages such as high safety, low cost and environmental friendliness. Remarkable progresses of aqueous sodium-ion batteries gradually encourage their process of industrialization. However, compared with the organic secondary ion batteries, the development of aqueous sodium-ion batteries is limited by the narrow stable voltage window of the electrolyte and the poor cycle stability of the electrode material. How to solve these problems is still the key to the development of aqueous sodium-ion batteries. The latest developments in electrode materials, electrolyte and current collector of aqueous sodium-ion batteries, as well as challenges and possible solutions for developing high-performance aqueous sodium-ion batteries are mainly summarized in this review. Furthermore, the development prospects of aqueous sodium-ion batteries are discussed.

Graphene, a monolayer of carbon atoms packed into a two-dimensional crystal structure, attracted intense attention owing to its unique structure and optical, electronic properties. Raman spectroscopy is a quick and precise method in material science and has been employed for many years to investigate material properties. It can be used to investigate the electronic band structure, the phonon energy dispersion and the electron-phonon interaction in graphene systems. In probing graphene's properties, Raman spectroscopy is considered to be a reliable method. In this review, we highlight recent progress of studying graphene structure using Raman spectroscopy. First, on the basis of systematically analyzing the phonon dispersion of graphene, the typical Raman scattering features of graphene, such as G band, G' band, and D band, and the basic physical process are introduced. Using these Raman fingerprints, we can quickly and directly distinguish the layer thickness of graphene, determine the edge chirality and monitor the type and density of defects in graphene. Second, stacking disorder will significantly modify the optical properties and interlayer coupling stretch of few-layer graphene so that the Raman features of graphene will be strongly influenced not only in the G band intensity but also in the intensity, lineshape and the frequency of G' band. According to the peak position, width, and intensity of the Raman G band and G' band in graphene, we also discuss the influence of doping, substrate, temperature, and strain on the electronic structure of graphene. Finally, we introduce the second order overtone and combination Raman modes and the low frequency Raman feature (shear and layer breathing mode) in graphene, and discuss the dependence of these peaks on the structure of graphene.

Fluoroorganic compounds, especially chiral fluorinated compounds, are of importance in the pharmaceutical and agrochemical industries as well as in the development of functional materials and related areas. It has been a challenge for organic chemists to enantioselectively introduce a fluorine atom into one molecule. In recent years, enantioselective fluorinations have made significant progresses under chemists’ continuous efforts. Chiral nonracemic fluoro-organic molecules with a fluorine atom on a stereogenic center are readily prepared via chiral electrophilic fluorinating reagent-mediated enantioselective fluorinations, substrate-controlled enantioselective electrophilic fluorinations, chiral metal complexes and asymmetric catalyst—directed catalytic enantioselective fluorinations. Especially, chiral metal complexes and organo-catalysts in combination with electrophilic fluorinating reagents have found applications to the synthesis of a variety of chiral fluoroorganic compounds. This review will cover in detail the methods, strategies and re-cent developments in enantioselective electrophilic fluorinations, and discuss their applications and limita-tions of these asymmetric fluorination methods.

The synthesis, development and application of the new supramolecular host-pillar[n]arene in recent four years are reviewed. Two main synthetic strategies were employed in the synthesis of pillar[n]arene and its derivatives: “firstly cyclization then modification” and “firstly modification then cyclization”. Owing to its special conformational structures and physical and chemical properties, pillar[n]arene has been mainly applied to the fields such as host-guest complex and molecular recognition, construction of assembly and smart materials.

A simple, efficient, inexpensive and powerful method for the C—N coupling of nitrogen-containing heterocycles with aryl halides was developed by using cheap Cu₂O as catalyst, inexpensive and readily available 8-hydroxyquinoline as ligand, n-Bu₄NBr as phase transfer catalyst, water as solvent at 100℃. Most products were synthesized in good to excellent yields.

Fluorene and its derivatives are important compounds, which have biphenyl structure with rigid plane,as well as large π-conjugated system. These special structures of fluorene compounds endow their distinct various functions, properties and biological activities, as well as wide potential application in photoelectrical materials, medicinal agents and so on. More importantly, the fluorene compounds are easily modified and various functional groups could be conveniently introduced into the fluorene ring. The syntheses of fluorene derivatives and their potential applications were extensively investigated and have been become highly active highlight in recent years, and the progress is quite rapid. Combining with our researches and referring other works from literatures, this paper systematically reviews the recent advance in the research and development of fluorene in organic electro-luminescence materials, two-photon absorbing materials, photochromic materials, solar cells, medicinal chemistry and so on. The perspectives of the foreseeable future are also presented.

Vilsmeier reagents generated from amides and acyl halides have been found to be versatile in the organic synthesis because they have both electrophilicity and nucleophilicity. Some types of reactions under vilsmeier condition in recent years are reviewed in this paper. The paper focuse on the, acylation, chlorination, chloroformylation, aromatization, annulation and dehydration and so on.

A review with 24 refs. The generally accepted mechanisms for the Grignard reactions of ketones are described. Evidences supporting the single electron transfer (SET) process in some of the reactions under certain conditions are presented. Some main factors, including structure of reactants, nature of solvents and effect of transition-metal impurities, which might affect the course and mechanism (ionic and/or SET) of the reactions are also discussed.6

Four natural flavonoids 3'-O-methyldiosmetin (1), diosmetin-7-O-β-D-glucoside (2), diosmetin-7-O-β-D-galactoside (3), 3'-O-methyldiosmetin-7-O-β-D-glucoside (4), and eight new diosmetin derivatives 3'-O-methyldiosmetin-7-O-β-D-galactoside (5), diosmetin-7-O-β-D-acetylglucoside (6), diosmetin-7-O-β-D-acetylgalactoside (7), 3'-O-methyl- diosmetin- 7-O-β-D-acetylglucoside (8), 3'-O-methyldiosmetin-7-O-β-D-galactoside (9), 7-O-isopentyldiosmetin (10), 7-O-prenyldiosmetin (11) and 7-O-farnesyl-3'-O-methyldiosmetin (12) were synthesized from hesperidin by reaction steps including dehydrogenation, selective methylation, glycoside hydrolysis, glycosylation under phase transfer catalytic condition, O-prenylation and O-farnesylation, respectively. Their structures were confirmed by NMR, IR and MS techniques. The synthesized compounds were evaluated for biological activity against four human cancer cell lines by the standard MTT [3-(4,5-dimethylthiazol-2-y1)-2,5-diphenytetrazolium bromide] method, and the results showed that 6, 10 and 11 exhibited moderate cytotoxicity against SMMC-7721, MCF-7 and SW480 cancer cell lines.

The key intermediate ethyl 5-methyl-3-(quinoxalin-2-yl)-isoxazole-4-carboxylate (4) was obtained by 1,3-dipolar cycloaddition reaction of 2-(1-hydroxylimino-1-chloro-methyl)-quinoxaline (3) with sodium 1-aceto-1-ethoxycarbonyl-methide, which was converted to hydrazide 5 by treating with hydrazine hydrate. Condensation of 5 with aromatic aldehydes gave corresponding hydrazones 6, then cyclization of 6 in Ac2O afforded 1,3,4-oxadiazolines 7a～7f. Thiosemicarbazides 8 prepared by treatment of the hydrazide 5 with suitable isothiocyanates, were cyclized in 1 mol•L－1 NaOH aqueous solution to give 5-thio-1,2,4- triazolines 9, and the Mannich base 10a～10f, 11a～11f and 12a～12f were synthesized. Their structures were analyzed and established by elemental analysis, IR, 1H NMR and MS spectra.

This paper reviewed the recent advances of Glaser coupling reaction and its applications to the synthesis of conjugated polymers. The reaction mechanism was also discussed.

Chiral auxiliaries controlled asymmetric reaction is one of the main methods in asymmetric synthesis. Under the control of the Evans auxiliary and catalyzed by FeCl₃, different Grignard reagents were added asymmetrically to the substrates 1 by the way of 1,4-Michael addition reaction, and a series of Michael addition products 2a～2h which containing two chiral centers have been synthesized with higher stereoselectivity. Among them, compounds 2d and 2e achieved high diastereospecifically up to 98% de. The results showed that the steric hindrance of the Grignard reagents is the main factor which influences the stereoselectivity of Micheal addition.

This paper reviews the advances in the 1,3-dioplar cycloadditions between nitrones and alkenes catalyzed by chiral Lewis acid.

This paper reviews the recent progress of all kinds of reductive amination methods and their applications in organic synthesis, particularly emphasis on the introduction to the reductive amination with high efficiency and high selectivity.

CO₂ is an ideal C1 source in chemical transformations. It is of great significance to utilize CO₂ in chemical conversion to synthesize high value-added compounds, including carboxylic acids and carbonyl-containing heterocycles. On the other hand, the difunctionalization of olefins is an important organic reaction, which can efficiently convert easily available olefins into important compounds with structural diversity. However, due to the low reactivity of CO₂ and the difficulty in controlling the selectivity, the difunctionalization of olefins with CO₂ is highly challenging. Recently, the significant progress of radical chemistry has provided new strategies and promoted the development of novel transformations in this field. This Perspective summarizes the recent progress of the radical-type difunctionalization of olefins with CO₂, including the oxy-alkylation, carbocarboxylation, silacarboxylation, thiocarboxylation, and dicarboxylation of alkenes with CO₂. At the same time, we also highlight the mechanism with radicals and four kinds of pathways are proposed: (1) Free radicals attack olefins to form new carbon radical intermediates. The radicals are then oxidized to form carbocations, which are further captured by carbonates or carbamates. It is also possible for direct C—O bonding reaction or sequent C—I and C—O bonds formation. (2) The new carbon radical intermediates, in-situ generated through attack of alkenes with radicals, are reduced via single electron transfer into carbanions, which could attack CO₂ to form C—C bonds. (3) CO₂ is reduced into CO₂ radical anions in the highly reductive reaction conditions. Once generated, the CO₂ radical anions might attack olefins to form carboxylate bearing more stable carbon radical intermediates (such as benzylic ones) and further form C—C bonds or carbon-heteroatom bonds. (4) Olefins are reduced via single electron transfer into alkenyl free radical anions in the highly reductive reaction conditions. These anions may attack CO₂ to form carboxylate bearing carbon radical intermediates and are further reduced to generate carbanions. Finally they may attack another CO₂ to form succinic acid derivatives. We point out the challenges and predict the future development in the field, including the more challenging substrates, more reaction types, better selectivities, and deeper mechanistic understanding.

The synthetic methods for ibuprofen, an anti-inflammatory drug, are introduced. Emphases are Boots/ Hoechst-Celanese (BHC) process with the fame of cleaner prodution and the recent progress on synthesis of ibuprofen with green methodology. Especially the environmentally friendly recovery of catalyst and the asymmetric carbonylation of p- isobutylstyrene for preparing ibuprofen are reviewed.