Arylsulfonate-based nucleophile assisting leaving groups

[Chemical reaction: See text] The synthesis and unique reactivity of a series of arylsulfonate-based nucleophile assisting leaving groups (NALG) containing oligomeric ether units (including crown ethers) attached to the arylsulfonyl ring in the ortho orientation are described. The reactions of a variety of these ether-containing alkyl sulfonates with metal halides proceeded at substantially greater rates than electronically similar sulfonates. These ether-containing leaving groups also displayed marked selectivity for lithium halides relative to the corresponding sodium and potassium salts in nucleophilic displacement reactions.     

Regioselective synthesis of (E)-3-[2-(arylmethylene)-1-(arylsulfonyl)hydrazino]-2-propenoates via the reaction of arylsulfonyl hydrazones and alkyl propiolates in the presence of triphenylphosphine

A regioselective method for the synthesis of (E)-3-[2-(arylmethylene)-1-(arylsulfonyl)hydrazino]-2-propenoates is described. The reaction takes place between arylsulfonyl hydrazones and alkyl propiolates in the presence of triphenylphosphine as the catalyst.     

Novel trifunctional building blocks for fluorescent polymers

[reaction: see text] Herein, we describe the synthesis of fluorescent 2-(arylsulfonyl)methacrylates and its polymers. These novel trifunctional monomers, possessing a fluorescent arylsulfonyl (ArSO(2)) group, an alkyl group (R), and a polymerizable olefin, serve as useful building blocks for functionalized fluorescent polymers.     

2-烷基-2-(芳磺酰基)乙酸酯的高效共轭加成

本文报道在固-液相转移催化的温和条件下2-烷基-2-(芳磺酰基)乙酸酯(1)与α, β-不饱和酯、腈、酮(2)的高选择性和高效率共轭加成反应。成功地合成了2, 2-二取代戊二酸二酯(3a~d)、4-氰基丁酸酯(3e~g)和5-氧代己酸酯(3h~j)。对它们的结构作了表征。初步讨论了本合成法的特点。Michael受体、相转移催化剂和溶剂等对共轭加成反应的影响。     

Synthesis of diaryl disulfides via the reductive coupling of arylsulfonyl chlorides

A facile synthesis of diaryl disulfides from arylsulfonyl chlorides in the presence of triphenylphosphine has been developed.     

Synthesis of bis(arylsuh'onyl)furoxans from aryl nitromethyl sulfones

The synthesis of some symmetrically substituted bis(arylsulfonyl)furoxans from aryl nitromethyl sulfones is reported.     

Novel C-H functionalization of arenes: palladium-catalyzed synthesis of diaryl sulfides

A novel protocol for the direct arylthiolation of electron-rich arenes is described. Applying arylsulfonyl cyanides in the presence of catalytic amounts of Pd allows for a straightforward synthesis of diaryl sulfides.     

An Efficient Synthesis of N-Arylsulfonylindoles from Indoles and Arylsulfonyl Chlorides in the Presence of Triethyl-benzylammonium Chloride (TEBA) and NaOH

An efficient synthesis of N‐arylsulfonylindoles from indoles and arylsulfonyl chlorides in the presence of triethylbenzylammonium chloride (TEBA) and NaOH at room temperature is described.     

Desulfinative palladium‐catalyzed cross‐coupling of arylsulfonyl hydrazides with aryl bromides under air

A highly efficient and mild palladium‐catalyzed cross‐coupling of arylsulfonyl hydrazides and aryl bromides for the selective synthesis of unsymmetrical biaryls has been developed. This methodology has the advantages of easily accessible starting materials, functional group tolerance and a wide range of substrates, which provide rapid access to biaryls derivatives. In this protocol, abundant and stable aryl bromides serve as the aryl sources by coupling reaction of the aryl group generated from arylsulfonyl hydrazides via in situ release of nitrogen and sulfur dioxide. No external oxidants or acids are needed for this kind of transformation.     

Synthesis of 1-Arylsulfonylpyrroles

The synthesis of 1-arylsulfonylpyrroles is normally accomplished by the condensation of an arylsulfonyl chloride with pyrrolylpotassium.¹ We wish to report a facile synthesis of 1-arylsulfonylpyrroles which is versatile, proceeds in moderate to good yield and eliminates the necessity of using pyrophoric potassium.     

Facile synthesis of N-(arylsulfonyl)-4-ethoxy-5-oxo-2, 5-dihydro-1H-pyrolle-2, 3-dicarboxylates by one-pot three-component reaction

Three-component reaction of arylsulfonamides,dialkyl acetylenedicarboxylates,and ethyl chlorooxoacetate promoted by triphenylphosphine and triethylamine provides a sufficient route for the synthesis of dialkyl N-(arylsulfonyl)-4-ethoxy-5-oxo-2,5-dihydro -1H-pyrolle-2,3-dicarboxylates in good yields.     

Pd(OAc)2/PPh3-Catalyzed Desulfonylative Homocoupling of Arylsulfonyl Chlorides

The Pd‐catalyzed homodimerization with respect to arylsulfonyl chlorides as an efficient method for the synthesis of biaryls has been developed. This desulfonylative reaction which was performed at reflux in 1,4‐dioxane for 4 h under air afforded the desired products in good to excellent yields.     

Oxamates derived from 5-aminopyrazoles

Several oxamates were prepared from ethyl oxalyl chloride and 5-amino-4-cyanopyrazoles substituted in the 1-position with aryl, aroyl and arylsulfonyl groups. Both aroyl and arylsulfonyl groups suffered chloride-induced cleavage during this process. The synthesis of 7-(6-chloro-3-pyridazinyl)-7H-pyrazolo[3,4-d]-1,2,3-tri-azin-4(3H)-one ( 11 ) and its reaction with methanol to give 1-(6-chloro-3-pyridazinyl)-5-methoxy-1H-pyrazole-4-carboxamide ( 12 ) are also reported. A mechanism for this interesting transformation is presented.     

Unsymmetrical diaryl sulfones through palladium-catalyzed coupling of aryl boronic acids and arylsulfonyl chlorides

[reaction: see text] A simple and efficient method for the synthesis of unsymmetrical diaryl sulfones using the palladium-catalyzed coupling of aryl boronic acids and arylsulfonyl chlorides has been developed. High product yields, a short reaction time, and mild reaction conditions are important features of this method.     

Direct synthesis of 6-sulfonylated phenanthridines via silver-catalyzed radical sulfonylation-cyclization of 2-isocyanobiphenyls

A convenient and straightforward synthesis of 6-sulfonylated phenanthridines via silver-catalyzed sequential radical insertion, cyclization and aromatization of 2-isocyanobiphenyls is reported. The protocol does not require a phenanthridine scaffold as a substrate and presents a highly regioselective synthesis of 6-alkyl/arylsulfonyl phenanthridines. The protocol utilizes readily available and easy to handle sodium sulfinates as sulfonating agents and potassium persulfate as an oxidant to afford good to excellent yields of the desired products in a one-pot operation at room temperature.     

Synthesis of di(hetero)aryl sulfides by directly using arylsulfonyl chlorides as a sulfur source

A new, efficient protocol for the synthesis of di(hetero)aryl sulfides is described. Cheap and easily available arylsulfonyl chlorides as a sulfur source reductively couple with electron-rich (hetero)arenes (e.g., indolizines, indoles, electron-rich benzenes, etc.) in the presence of triphenylphosphine to afford di(hetero)aryl thioethers in good yields.     

Persulfonylation of amines applied to the synthesis of higher generation dendrimers

Systematic analysis of the persulfonylation of branched aromatic oligoamines with different arylsulfonyl chlorides allowed optimization of the repetitive steps involved in the synthesis of the sulfonimide-based dendrimers. The optimized procedures afforded the fourth generation N- and pentaphenylene-centered dendrimers with 16 and 32 peripheral groups, respectively. Analysis of products of incomplete substitution showed that the amino groups in aromatic oligoamines are persulfonylated consecutively.     

Synthesis of 1-(arylsulfonyl)pyrrolidines from phenols and 1-[(4-chlorophenyl)sulfonyl]-2-ethoxypyrrolidine

Acid-catalyzed reaction of 1-[(4-chlorophenyl)sulfonyl]-2-ethoxypyrrolidine with phenols leads to the formation of new 1-(arylsulfonyl)pyrrolidines. The reaction proceeds under mild conditions and may be used as a convenient method for the synthesis of pyrrolidine-1-sulfonylarene derivatives containing a phenol fragment in the position 2.     

Regioselective single-reactor synthesis of arylsulfonyl derivatives of 3,5-diamino-1,2,4-triazole

Arylsulfonylation of 1-acetyl-3,5-diamino-1,2,4-triazole with arylsulfonyl chlorides in pyridine, with the subsequent hydrolysis of the acetyl group, was studied; a new regioselective method for synthesis of N-(5-amino-1H-1,2,4-triazol-3-yl)arylsulfonamides was developed.     

倍半硅氧烷改性环氧树脂的研究进展

倍半硅氧烷是近年发展起来的一种分子水平的有机无机杂化材料。文章介绍了倍半硅氧烷的结构、合成以及笼型倍半硅氧烷（POSS）基高分子复合材料的结构及合成方法。倍半硅氧烷改性聚合物可以提高聚合物的热性能、阻燃性能和物理机械性能等。文章综述了倍半硅氧烷改性环氧树脂的研究进展。