Stereoselective synthesis of 3-aminoindan-1-ones and subsequent incorporation into HIV-1 protease inhibitors

A new method for the stereoselective synthesis of 3-aminoindan-1-ones from triflates of salicylic sulfinyl imines and ethylene glycol vinyl ether has been developed. The reaction sequence starts with a regioselective Heck reaction followed by stereoselective Lewis acid mediated annulation. Acidic cleavage of the sulfinamides produced pure (R)- and (S)-3-aminoindan-1-ones, which were successfully isolated and incorporated into active HIV-1 protease inhibitors.     

Asymmetric synthesis of sulfinamides using (-)-quinine as chiral auxiliary

A process has been designed and demonstrated for the asymmetric synthesis of sulfinamides using quinine as auxiliary. A variety of chiral sulfinamides including N-alkyl sulfinamides with diverse structure were prepared in good yields and excellent enantioselectivity starting from easily available and inexpensive reagents. The auxiliary quinine could be recovered and recycled.     

Cyclic Sulfinamides

The literature on cyclic sulfinamides (put simply, sultims) published from 1989 to 2022 has been summarized and reviewed. The information is divided into two sections: the analysis of synthetic methods on the preparation of cyclic sulfinamides and the discussion of the chemical properties of cyclic sulfinamides focusing on their reactions and applications. The survey of the reaction conditions, provided in the most detailed way, and a critical view of the reaction mechanisms add an extra dimension to the text. The data presented will be useful to specialists in different areas, especially those who work in the field of synthetic organic and pharmaceutical chemistry.     

Access to Highly Functionalized Sulfonated Cyclopentanes by Acid‐Promoted Rauhut–Currier Reaction with Sulfinamides

An unexpected acid‐mediated cascade reaction induced by conjugate addition of sulfinamides to dienediones has been developed. This highly efficient Rauhut–Currier reaction enables the rapid, high‐yielding construction of sulfonated cyclopentanes with three contiguous stereogenic centers in a single operation starting from simple sulfinamides. This process constitutes the first example of sulfinamide‐promoted cycloisomerization.     

An Optimized Ni-catalyzed Chan-Lam Type Coupling: Enantioretentive Access to Chiral N-Aryl Sulfinamides

C−N bond formation takes on a critical significance in reactions of organic synthesis, material production and pharmaceutical manufactory. Chan-Lam has proposed a useful methodology to furnish secondary arylamides under mild conditions. However, when chiral sulfinamides serve as the coupling precursors, the Cu-catalyzed coupling reaction is found with low efficacy. Complex side-products are generated under classic conditions. Moreover, it led to the racemization of the coupling product. In this study, an optimized Ni-catalyzed Chan-Lam type coupling conditions were proposed, which resulted in clean conversion from chiral sulfinamides and arylboronic acids to offer N-aryl sulfinamides efficiently and enantioretentively. The trans-N¹,N²-dimethylcyclohexane-1,2-diamine was proven as the most efficient ligand. Under the optimized conditions, a series of chiral N-aryl sulfinamides was prepared with high chemical yield without racemization. Furthermore, a plausible and novel mechanism was proposed. Interestingly, the method could efficiently furnish a wide variety of C−X bonds by coupling arylboronic acids with different nucleophiles.     

Vinyl sulfone- and vinyl sulfoxide-modified tetrahydrofurans: a preliminary account of the enantiomeric synthesis of and diastereoselectivity of addition to new classes of Michael acceptors

Enantiomerically pure 2-hydroxymethylene substituted-2,5-dihydro-3-(arylsulfonyl)- and 2-hydroxymethylene substituted-2,5-dihydro-3-(arylsulfinyl)-furans have been prepared from easily accessible carbohydrate derivatives for the first time. The strategy for accessing both these sulfones and sulfoxides is more efficient than the methods reported so far for the synthesis of this type of compounds. Hydroxymethylene group is sufficient to impose diastereoselectivity on the addition of a wide range of nucleophiles to vinyl sulfone-modified tetrahydrofurans. The benzyl protected hydroxymethylene group also suppresses the influence of chirally pure sulfoxides as two diastereomeric vinyl sulfoxide-modified tetrahydrofurans afforded the Michael adducts with same configurations at C-3 and C-4; this has been established by oxidizing the adducts, which were found to be identical to the products obtained by adding the same nucleophiles to the corresponding vinyl sulfones. These highly reactive Michael acceptors may be considered as a new addition to the arsenals of synthetic chemists interested in the functionalization of tetrahydrofurans.     

Electron-transfer polymers. XXVIII. Synthesis of vinyl hydroquinone derivatives by means of the wittig reaction

The Wittig reaction has been applied to unsubstituted, monomethyl-, 3,6-dimethyl-, and trimethyl-2,5-dimethoxybenzyl chlorides to produce in quantitative to good yields the corresponding vinyl monomers, unsubstituted, monomethyl-, 3,6-dimethyl-, and trimethyl-2,5-dimethoxystyrenes. The reaction is applicable also to 2,5-dimethoxy-4-methylbenzaldehyde, and to O,O′-bis-(methoxymethyl)resorcinol-4-aldehyde to yield the corresponding vinyl monomers. The reaction is particularly suitable with all these compounds because it is run at room temperature or below and gives good to quantitative yields.     

Chiral sulfinamide/achiral sulfonic acid cocatalyzed enantioselective protonation of enol silanes

The application of chiral sulfinamides and achiral sulfonic acids as a cocatalyst system for enantioselective protonation reactions is described. Structurally simple, easily accessible sulfinamides were found to induce moderate-to-high ee's in the formation of 2-aryl-substituted cycloalkanones from the corresponding trimethylsilyl enol ethers.     

Copper-catalyzed rearrangement of vinyl oxiranes

A novel copper-catalyzed vinyl oxirane ring expansion protocol has been developed. A wide range of vinyl oxiranes can be rearranged to 2,5-dihydrofurans in excellent yields in the presence of electrophilic copper(II) acetylacetonate catalysts. Regioisomeric vinyl oxiranes can be converted to a single dihydrofuran product using these conditions. This method uses low catalyst loadings (0.5-5 mol %), has good tolerance of substitution patterns, and can be done in the absence of solvent.     

Electrochemical oxidation of N-p-toluenesulfinamides

[reaction: see text] Contrasting and interesting electrochemical behavior is observed in anodic oxidation of N-substituted p-toluenesulfinamides under controlled current conditions. For sulfinamides derived from secondary alkylamines and primary arylamines, the N-sulfinyl group is removed and the corresponding amines are formed; for sulfinamides derived from primary alkylamines, sulfur oxidation yields the corresponding sulfonamides in good yields.     

Stereospecific ring expansion of chiral vinyl aziridines

In this report, it is demonstrated that chiral vinyl aziridines can be stereospecifically ring expanded. This synthetic approach allows controlled access to chiral 2,5-cis- or 2,5-trans-3-pyrroline products from starting materials with the appropriate aziridine geometry. Twenty three ring expansion examples, most of which feature a stereospecific cyclization, are presented.     

Stepwise unidirectional synthesis of oligo phenylene vinylenes with a series of monomers. Use in plastic solar cells

Four new monomers for directional stepwise synthesis of oligophenylenevinylenes (OPVs) (4-{2-[4-(5,5-dimethyl[1,3]dioxan-2-yl)-2,5-dipropoxyphenyl]vinyl}benzyl)phosphonic acid diethyl ester, (5-{2-[4-(5,5-dimethyl[1,3]dioxan-2-yl)-2,5-dipropylphenyl]vinyl}thiophene-2-ylmethyl)phosphonic acid diethyl ester, (5-{2-[4-(5,5-dimethyl[1,3]dioxan-2-yl)-2,5-dipropoxyphenyl]vinyl}thiophene-2-ylmethyl)phosphonic acid diethyl ester, and (7-{2-[4-(5,5-dimethyl[1,3]dioxan-2-yl)-2,5-dipropylphenyl]vinyl}benzo[1,2,5]thiadiazol-4-ylmethyl)phosphonic acid diethyl ester have been prepared. Trimeric OPVs were then synthesized and tested as active materials in photovoltaic cells. Conversion efficiencies in the range of 0.5-1% were obtained in blends with the soluble C(60) derivative PCBM. A terpyridine end-functionalized trimer and a heterotrimer with a mixed composition of monomers were also prepared.     

C-H Bond activation and C-C bond formation in the reaction of 2,5-dimethylthiophene with TpMe2Ir compounds

The bulky 2,5-dimethylthiophene (2,5-Me2T) reacts at 60 degrees C with TpMe2Ir(C2H4)2 to give a mixture of two TpMe2Ir(III) hydride products, 3 and 4, that contain in addition a thienyl (3) or a thienyl-derived ligand (4). For the generation of 3 only sp2 C-H activation is needed, but the formation of 4 requires also the activation of an sp3 C-H bond and the formation of a new C-C bond (between vinyl and thienyl fragments). In the presence of 2,5-Me2T, compound 4 reacts further to produce a complex thiophenic structure (5, characterized by X-ray methods) that derives formally from two molecules of 2,5-Me2T and a vinyl fragment. Compounds 3-5 can be readily protonated by [H(OEt2)2][BAr'4](Ar'= 3,5-C6H3(CF3)2), with initial generation of carbene ligands (in the case of 3 and 5) as a consequence of H+ attack at the beta-carbon of the Ir-thienyl unit. Free, substituted thiophenes, derived from the original 2,5-Me2T, may be isolated in this way.     

Hydrolysis rates of alkyl and aryl sulfinamides: evidence of general acid catalysis

Sulfinamides are important in enantioselective synthesis, as rare post-translational modifications of proteins and as isosteres of the amide bond. Little is known about the rates of hydrolysis for aliphatic sulfinamides or the mechanism of hydrolysis. In this Letter, we show that sulfinamides hydrolyse by predominantly a non-specific acid/base catalysis with phosphate buffer but by varying the buffer concentration, it was possible to determine the hydrolysis rates of a range of sulfinamides with water through non-linear least squares regression.     

Reaction of Some Dibromomethyl-Substituted Cyclohexadienones with Molecular Bromine

4-Dibromomethyl-4-methyl-2,5-cyclohexadienone and its 2- and 3-methyl-substituted derivatives react with an equimolar amount of molecular bromine in carbon tetrachloride, yielding vinyl bromination products at the -position with respect to the carbonyl group. The reaction of 4-dibromomethyl-3,4-dimethyl-2,5-cyclohexadienone with a large excess of bromine, apart from the vinyl bromination product, gives the corresponding 3-bromomethyl and 3-dibromomethyl derivatives. 4-Dibromomethyl-2,4-dimethyl-2,5-cyclohexadienone takes up bromine molecule at the C ² ÍC ³ double bond.     

Application of sulfonyl chlorides and chiral amines in the efficient synthesis of nonracemic sulfinamides

A simple protocol that allows the preparation of separable epimeric sulfinamides from chiral amines and sulfonyl chlorides reduced in situ with triphenylphosphine in the presence of KOH is described. Using this method, tosyl chloride and nosyl chloride were successfully reacted with α-substituted primary amines to give five diastereomeric pairs, in certain cases accompanied by a small amount of the corresponding sulfonamide. Enantiopure products were isolated by column chromatography. The obtained enantiomerically pure sulfinamides were tested as organocatalysts in the asymmetric epoxide ring opening.     

Synthesis of Poly（p-phenyleneethynylene）s with Crosslinkable End or Side Groups and Its Solid State Structure and Optical Properties Before and after Crosslinking

Two crosslinkable poly(p-phenyleneethynylene)s(PPEs): poly[2,5-di(2'-ethyl-hexyloxy)-1,4-phenylenee-thynylene] with end-capped vinyl(PPE1) and poly[2,5-di(allyloxy)-1,4-phenyleneethynylene-2,5-di(2'-ethyl-hexyloxy)-1,4-phenyleneethynylene](PPE2) were synthesized. Via the thermal addition reactions of vinyl end groups of PPE1 and allyloxy side groups of PPE2, crosslinked polymers C-PPE1 and C-PPE2 were obtained, respectively. The two polymers were characterized by wide-angle X-ray diffraction(WXRD), ultravio...     

Lewis acid-catalyzed reactions of donor-acceptor cyclopropanes with furan derivatives

Lewis acid-catalyzed reactions of dialkyl 2-arylcyclopropane-1,1-dicarboxylates with 2,5-dimethylfuran were found to give products of [3+2]-cycloaddition to C(2)-C(3) bond, which contain reactive vinyl ether moiety. These adducts can be further transformed into various products depending on the Lewis acid, the nucleophilicity of aryl group in starting cyclopropane and the ratio of reagents. The vinyl ether moiety can attack the appropriate nucleophilic center in intramolecular or intermolecular mode or can undergo cycloaddition to the second equivalent of donor-acceptor cyclopropane. Alternatively, 2,5-diphenylfuran formed Friedel-Crafts products only when reacted with donor-acceptor cyclopropanes.     

New polymer syntheses. LXXV. 2,5-biaryloxyterephthalic acids and rigid-rod polyaramides derived from them

Several 2,5-bisaryloxyterephthalic acids were prepared by a new method, namely arylation of diethyl-2,5-bistrimethylsiloxyterephthalate. Rigid-rod polyaramides were prepared by polycondensation of silylated diamines with a terephthaloylchloride with two diphenylsulfone side chains. Another polyamide was prepared from 2,5-bis(4′-cyanophenoxy) terephthalic acid and 1,4-diaminobenzene. None of these polyaramides is meltable and their solubilities differ largely. A copolymer of 1,4-diaminobenzene and 3,3′-dimethoxybenzidine is soluble in various organic solvents including polar vinyl monomers. © 1994 John Wiley & Sons, Inc.     

2,5-二[4-(2-芳基乙烯基)苯基]噁二唑的合成及发光特征

二乙烯联苯及其衍生物是一种可发射蓝光的小分子空穴型有机发光材料, 通过Wittig-Horner反应, 将电子传输型噁二唑环“嵌入”其中, 设计合成了6个2,5-二[4-(2-芳基乙烯基)苯基]-1,3,4-噁二唑化合物. 经光谱分析和元素分析等方法确认了它们的化学结构. IR和UV-vis分析数据表明标题化合物分子结构中的C＝C双键均为反式结构特征. 研究结果表明: 2,5-二[4-(2-对二甲氨基苯基乙烯基)苯基]-1,3,4-噁二唑具有良好的蓝色发光性能; 取代基对标题化合物的UV-vis吸收光谱和发光特性的影响显着.