Organosulphur compounds-lxix1 optically active sulphinates: a new type of enantioselective asymmetric synthesis and kinetic resolution2

Optically active sulphinates with the sulphur atom as a sole centre at chirality are prepared by two methods. The first involves the reaction of symmetrical sulphites with tert-butylmagnesium chloride in the presence of optically active aminoalcohols. This new asymmetric, enantioselective synthesis affords t-butylsulphinates with 40–70% enantiomeric excess values. The second approach is based on a new type of kinetic resolution taking place when racemic sulphinates are reacted with tert-butylmagnesium chloride complexed by optically active alkaloid bases. Both the recovered sulphinates and sulphoxides formed in this reaction show moderate optical purities.     

New aromatic azo compounds: syntheses and liquid-crystalline properties

The chemical syntheses of 12 new azo dyes are reported. The optically active compounds were prepared by the Mitsunobu reaction, amide formation, and esterification with optically active alcohols or acids. Several new compounds showed liquid-crystalline properties, and their phase transition behavior was investigated.     

Regulation of Electrocatalytic Activity by Local Microstructure: Focusing on the Catalytic Active Zone

Traditional regulation methods of active sites have successfully optimized the performance of electrocatalysts, but seem unable to achieve further breakthrough in the catalytic activity. Unlike the conventional viewpoint of focusing on single active site, the concept of local microstructure active zone is more comprehensive and new methods to regulate the reaction zone for electrocatalytic reactions are developed accordingly. The local microstructure active zone refers to the zone with high catalytic activity formed by the interaction between active atoms and neighboring coordination atoms as well as the surrounding environment. Instead of the traditional single active atom site, the active zone is more suitable for the actual electrochemical reaction process. According to this concept, the activity of electrocatalysts can be coordinated by multiple active atoms. This strategy is beneficial for understanding the relationship between material, structure, and catalysis, which realizes the design and synthesis of high-performance electrocatalysts. This review provides the research progress of this strategy for electrocatalytic reactions, with emphasis on their applications in oxygen evolution reaction, urea oxidation reaction, and carbon dioxide reduction.     

Original TDAE strategy using α-halocarbonyl derivatives

We report herein the selective C-C bond formation by the reaction of nitrobenzyl carbanions, formed via the TDAE strategy, with α-haloesters and α-haloamides. This reaction, extended in benzodioxole and dimethoxybenzene series provides new potentially CNS active agents.     

Carbon-carbon bonds by hydrolytic enzymes

Enzymes are efficient catalysts in synthetic chemistry, and their catalytic activity with unnatural substrates in organic reaction media is an area attracting much attention. Protein engineering has opened the possibility to change the reaction specificity of enzymes and allow for new reactions to take place in their active sites. We have used this strategy on the well-studied active-site scaffold offered by the serine hydrolase Candida antarctica lipase B (CALB, EC 3.1.1.3) to achieve catalytic activity for aldol reactions. The catalytic reaction was studied in detail by means of quantum chemical calculations in model systems. The predictions from the quantum chemical calculations were then challenged by experiments. Consequently, Ser105 in CALB was targeted by site-directed mutagenesis to create enzyme variants lacking the nucleophilic feature of the active site. The experiments clearly showed an increased reaction rate when the aldol reaction was catalyzed by the mutant enzymes as compared to the wild-type lipase. We expect that the new catalytic activity, harbored in the stable protein scaffold of the lipase, will allow aldol additions of substrates, which cannot be reached by traditional aldolases.     

Syntheses of stereoregular and optically active polyamides from active 4-chloro-1-benzotriazolyl diesters and diamines

A new route to prepare optically active polyamides was established, based on the polycondensation of two new active diesters: the active diesters of 4-chloro-1 hydroxybenzotriazole, such as 1,1'-(terephthaloyldioxy)bis(4-chloro-benzotriazole), and 1,1'-(isophthaloyldioxy)bis(4-chlorobenzotriazole), with optically active isomers of 2,4-diaminopentane. Dipolar aprotic solvents such as N,N-dimethylformamide and dimethyl sulfoxide were used as reaction solvents. The solution polycondensation carried out in solution at room temperature afforded optically active polyamides. The aminolysis of the two active diesters was carried out as a model reaction study.     

活性链末端的转化及其应用

综述了聚合反应中活性链末转化及其在分子构筑方面的最新应用进展。     

Application of 2-(2-chloroaroyl)methyleneimidazolidines in domino and multicomponent reaction: new entries to imidazo[1,2-a]pyridines and benzo[b]imidazo[1,2,3-ij][1,8]naphthyridines

A new strategy for the synthesis of tetrahydroimidazo[1,2-a]pyridines and unusual tetrahydrobenzo[b]imidazo[1,2,3-ij][1,8]naphthyridines has been successfully developed by cascade reactions including Knoevenagel condensation, aza-ene reaction, imine-enamine tautomerization, cyclocondensation/oxidation, and intramolecular S_NAr of precursors 2-(2-chloroaroyl)methyleneimidazolidines as new heterocyclic ketene aminals (HKA), which represent a class of polyfunctional scaffolds with four active reaction sites with aromatic aldehydes and malononitrile or ethyl 2-cyanoacetate under mild conditions. In this domino reaction, nine different active sites are involved, and two C-C bonds, two C-N bonds, and two new rings are constructed with all reactants efficiently utilized in the chemical transformation.     

A study of asymmetric hydrocyanation of heteroaryl carboxaldehydes catalyzed by (R)-oxynitrilase under micro-aqueous conditions

A number of new optically active heteroaryl cyanohydrins have been prepared by hydrocyanation under micro-aqueous conditions catalyzed by almond meal (containing (R)-oxynitrilase). Substituent effects on the reaction are discussed. This micro-aqueous method provides an efficient, convenient and economical approach to optically active cyanohydrins.     

N-(酰基二茂铁)苯并咪唑类化合物的合成和表征

将二茂铁磺酰氯或二茂铁甲酰氯和1H-苯并咪唑衍生物反应,合成了12个未见文献报道的N-(酰基二茂铁)苯并咪唑类化合物,用IR、1HNMR、元素分析和MS对其结构进行了表征。结果表明,含有活泼氢的苯并咪唑衍生物能与二茂铁酰氯生成相应的N-(酰基二茂铁)苯并咪唑衍生物,并有较好的收率。     

Synthesis and Antimicrobial Activity of New 4-Methyl-2-(3-pyridyl)thiazolyl Chalcones and Pyrazolines

Russian Journal of General Chemistry - In an attempt to develop active antimicrobial agents, a set of new thiazolyl chalcones has been synthesized by the Claisen–Schmidt reaction of...     

General route to racemic and enantiomeric carbo- and heterocyclic vinyl sulfoxides via tandem Michael addition/Horner olefination of alpha-phosphorylvinyl sulfoxides

A new one-pot synthesis of heterocyclic and carbocyclic vinyl sulfoxides has been developed which involves reaction of alpha-phosphorylvinyl sulfoxides with carbonyl compounds bearing oxygen, nitrogen, and carbon nucleophilic centers. Use of optically active alpha-phosphorylvinyl p-tolyl sulfoxides in this tandem Michael addition/Horner olefination reaction leads to the corresponding optically active cyclic sulfoxides. In this way, a variety of optically active chromene, pyrrolizine, chinoline, and cyclopentene sulfoxides have been efficiently prepared.     

A Novel Method for Biomimetic Synthesis of Mannich Bases

Since the early studies of Mannich, Mannich reaction has become an important tool for the synthesis of new compounds. Mannich bases can be either directly employed or used as intermediates. In this work, the one‐carbon unit transfer reaction of tetrahydrofolate coenzyme was initiated. 1,3‐Dimethylimidazolidine as a new tetrahydrofolate coenzyme model at formaldehyde oxidation level was used to react with ketone having active hydrogen atoms and amine to give the corresponding Mannich base in good yield by a covert Mannich reaction. A novel method for biomimetic synthesis of various Mannich bases is provided.     

Nucleophilic addition of nitrones to ketones: development of a new catalytic asymmetric nitrone-aldol reaction

A new organic reaction has been discovered in which nitrones react with carbonyl compounds in an aldoltype reaction to give functionalized beta-hydroxynitrones. The alpha-carbon atom of the nitrone undergoes a nucleophilic addition reaction to electron-deficient ketones, such as alpha-ketoesters, alpha,beta-diketones, and trifluoromethyl ketones, to afford the products in moderate to good yields. The scope and potential of the reaction have been investigated and developed. The reaction can also be catalyzed by secondary amines. The use of chiral cyclic amines, such as L-proline leads to optically active beta-hydroxynitrones in moderate yield and with moderate to high enantiomeric excess. The reaction mechanism was studied by kinetic measurements, intermediate and product analysis, and determination of the absolute configuration of the product; based on these investigations a mechanism for the new reaction is proposed.     

Synthesis and properties of novel diisocyanate based optically active polyimides

A new optically active diisocyanate was prepared from the reaction of l-leucine and pyromellitic dianhydride (PMDA) and subsequent transformation of intermediate imide-containing diacid to diisocyanate via Weinstock modification of Curtius rearrangement. Solution polycondensation reaction of the prepared diisocyanate with PMDA, 3,3,4,4-benzophenonetetracarboxylic dianhydride, and hexafluoroisopropylidene 2,2-bis(phthalic anhydride) resulted in the preparation of novel optically active polyimides. The optimal conditions for polyimidations (reaction duration and temperature programming) were obtained via study of the model compound. The monomer, model compound and polymers were characterized by FTIR, ¹HNMR, mass spectroscopy and elemental analysis and their optical and physical properties were studied as well.     

A new entry to asymmetric synthesis of optically active alpha,gamma-substituted gamma-butyrolactones, using a carbohydrate derived amide as both a chiral auxiliary and a proton source

A new entry for the asymmetric synthesis of optically active alpha,gamma-substituted gamma-butyrolactones was developed by using a carbohydrate-derived amide as both a chiral auxiliary and a proton source. Unlike the previously reported examples, the chiral auxiliary employed in this reaction also successfully functioned as a protonating agent. Excellent asymmetric induction could be achieved by this dual stereoselective control in the reaction process.     

Strained polycycles by H5C5x free-radical cascades

[reaction: see text] An H(5)C(5x)-type free-radical chain reaction selectively generates up to three new bonds and three new stereocenters in one pot. This previously unexploited strategy provides a straightforward route to the tricyclic cyclopenta[c]indene skeleton, present in a wide range of pharmacologically active natural products, and can significantly simplify the synthesis of other strained polycyclic structures by sidestepping protection, deprotection, and functional group interconversion steps.     

A highly active ionic liquid catalyst for Morita-Baylis-Hillman reaction

The Morita-Baylis-Hillman reaction is an efficient carbon-carbon bond forming reaction for the preparation of α-methylene-β-hydroxycarbonyl compounds. A new and highly active di-naphthalene imidazolium salt has been synthesized. We have found that 1,3-bis[2-(naphthalene-2-yloxy)propyl]imidazolium bromid promoted the Morita-Baylis-Hillman reaction of various aryl aldehyde compounds in the absence of solvents. Our studies show that the Morita-Baylis-Hillman reaction by the influence of ionic liquid to give a high yield and short reaction time.     

Asymmetric multicomponent copper catalyzed synthesis of chiral propargylamines

A three-component stereoselective reaction between an aldehyde, an amine and phenylacetylene to afford optically active propargyl amines in good yields was developed. The reaction is catalysed by copper complexes of enantiomerically pure bis-imines. The best results were obtained with imines readily prepared in very high yields from the commercially available binaphtyl diamine.

A very simple experimental procedure at room temperature allowed to obtain optically active propargyl amines in very good yields and enantioselectivity up to 75%. The extremely simple methodology and the mild reaction conditions, as well as the possibility of a modular approach for developing new and more efficient bis-imine-based chiral ligands make the present methodology very attractive.     

A Lewis acid-Lewis base bifunctional catalyst from a new mixed ligand

Covalent attachment of quinine to a salen framework through a racemic linker gave a new mixed ligand in a 1:1 diastereomeric mixture, from which an active Lewis acid-Lewis base (LA*-LB*) bifunctional catalyst derived from Co(II) was discovered by the screening of metal complexes. The remarkable intramolecular bifunctional catalytic activity (1 mol % catalyst loading) of the new catalyst was demonstrated using a proof-of-principle reaction. [reaction: see text].