One-Step Synthesis of Unsymmetrical Sulfides Bearing Hexafluorocumyl Moiety

A facile and convenient one-pot synthesis of novel unsymmetrical sulfides, 2′-alkylthio- and 2′-arylthio-1,1,1,3,3,3-hexafluoro-2-phenylpropan-2-oles 1a–k, is presented. Physicochemical characterization; IR infrared; ¹H, ¹³C, and ¹⁹F NMR; and mass spectral analyses of the obtained compounds are discussed as well.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]     

Synthesis of Some Dialkyl Bromo-Substituted Benzyl Phosphonates

Arbuzov reaction of bromo-substituted benzyl bromides and trialkyl phosphites in benzene gave high yields of dialkyl bromo-substituted benzyl phosphonates, and —CH₂CH₂CH₂CH₃). The structural assignments of these phosphonates were confirmed by ¹H nmr, ¹³C nmr, ir and mass spectral analysis.     

苄基锡烯或炔基膦酸酯的合成

合成了具有通式为（ＰｈＣＨ２Ｓｎ）ｎ－１Ｏ２Ｐ（Ｏ）Ｒ（ｎ＝２，３；Ｒ＝－Ｃ＝ＣＰｈ，－Ｃ＝ＣＣ５ｈ１１－ｎ，－Ｃ＝ＣＣＨ２ＯＣＨ３，－ＣＨ＝ＣＣＩＰＨ）的８个苄基锡烯或炔基膦酸酯，并通过元素分析、ＩＲ和１ＨＮＭＲ对其进行了表征。     

炔基苯甲酰胺衍生物的液相合成

液相合成兼容了固相合成可快速简便地对产物进行分离纯化以及溶液相合成可 在均相条件下进行反应和用常规手段对反应中间体进行分析检测的优点，用聚乙二 醇(PEG)4000作为可溶性聚合物支持体，通过醚键将[1，3，5]氯三嗪连接在PEG上 制备成PEG支持的新型的可溶性聚合物试剂I．该试剂在N-甲基吗啉的作用下与对碘 苯甲酸反应生成相应的活性酯中间体Ⅱ，该中间体继而在Pd(Ⅱ)／Cu(Ⅰ)共催化下 与端炔发生Sonogashira偶联反应得到另一中间体Ⅲ，在伯胺或仲胺的存在下进行 胺解反应得到炔基苯甲酰胺衍生物Ⅳ．由于PEG具有柔韧的长链而不会对链端连接 的反应中心的活性产生影响，因此该反应在均相体系中进行，不仅反应条件温和， 产率良好，而且反应还具有良好的选择性．实验发现，芳香胺和非芳香胺均可获得 良好的反应结果，但芳香胺所需的反应时间较长；伯胺和仲胺都是良好的胺解试剂 ，但使用仲胺时产率较低；N原子亲核试剂比O原子亲核试剂具有更大的反应性．此 外，PEG 4000支持的[1，3，5]氯三嗪试剂没有强烈的刺激性，可长期储存使用．     

One-Step Synthesis and Schlenk-Type Equilibrium of Cyclopentadienylmagnesium Bromides

In the in situ Grignard metalation method (iGMM), the addition of bromoethane to a suspension of magnesium turnings and cyclopentadienes [C₅H₆ (HCp), C₅H₅-Si(iPr)₃ (HCp^TIPS)] in diethyl ether smoothly yields heteroleptic [(Et₂O)Mg(Cp^R)(μ-Br)]₂ (Cp^R=Cp ( 1 ), Cp^TIPS ( 2 )). The Schlenk equilibrium of 2 in toluene leads to ligand exchange and formation of homoleptic [Mg(Cp^R)₂] ( 3 ) and [(Et₂O)MgBr(μ-Br)]₂ ( 4 ). Interfering solvation and aggregation as well as ligand redistribution equilibria hamper a quantitative elucidation of thermodynamic data for the Schlenk equilibrium of 2 in toluene. In ethereal solvents, mononuclear species [(Et₂O)₂Mg(Cp^TIPS)Br] ( 2’ ), [(Et₂O)_nMg(Cp^TIPS)₂] ( 3’ ), and [(Et₂O)₂MgBr₂] ( 4’ ) coexist. Larger coordination numbers can be realized with cyclic ethers like tetrahydropyran allowing crystallization of [(thp)₄MgBr₂] ( 5 ). The interpretation of the temperature-dependency of the Schlenk equilibrium constant in diethyl ether gives a reaction enthalpy ΔH and reaction entropy ΔS of −11.5 kJ mol⁻¹ and 60 J mol⁻¹, respectively.     

Photochemical Dual‐Catalytic Synthesis of Alkynyl Sulfides

A photochemical dual‐catalytic cross‐coupling to form alkynyl sulfides via C(sp)−S bond formation is described. The cross‐coupling of thiols and bromoalkynes is promoted by a soluble organic carbazole‐based photocatalyst using continuous flow techniques. Synthesis of alkynyl sulfides bearing a wide range of electronically and sterically diverse aromatic alkynes and thiols can be achieved in good to excellent yields (50–96 %). The simple continuous flow setup also allows for short reaction times (30 min) and high reproducibility on gram scale. In addition, we report the first application of photoredox/nickel dual catalysis towards macrocyclization, as well as the first example of the incorporation of an alkynyl sulfide functional group into a macrocyclic scaffold.     

Rapid Synthesis of Glycosyl Bromides by Ultrasound Irradiation

A convenient and environmentally friendly reactor for the synthesis of glycosyl bromides via ultrasound irradiation was designed. Peracetylated glycosyl bromides were synthesized from free saccharides by means of a one-pot method. Benzoylated and 6-subsituted glycosyl bromides were prepared from protected saccharides. The glycosyl bromides were obtained in isolated yields of 83% to 96%.     

A Sustainable Synthesis of 2‐Benzoxazyl and 2‐Benzothiazyl Ketones from Alkynyl Bromides and 2‐Amino(thio)phenols Promoted by a Recyclable Catalytic System

An environmentally and economically sustainable synthesis of 2‐benzoxazyl ketones and 2‐benzothiazyl ketones through FeCl₃·6H₂O catalyzed tandem reactions of alkynyl bromides with 2‐amino(thio)phenols in [bmim]BF₄ has been developed. Remarkable advantages of this new synthetic strategy include high efficiency, readily available starting materials, and recyclable catalyst and reaction medium.     

三苄基锡(IV)炔基(烯基)膦酸衍生物的合成及结构表征

烃基锡的膦（磷）酸衍生物具有较强的杀虫、杀菌及除草等生物活性,受到人们的极大关注［１,２］,尤其是三烃基锡（ＩＶ）二硫代磷酸酯的合成及应用研究已有较多报道［３,４］,但三烃基锡（ＩＶ）膦酸衍生物的合成研究很少［５］,而三烃基锡（ＩＶ）不饱和烃基膦酸衍生物Ｒ３ＳｎＯＰ（Ｏ）（ＯＨ）Ｒ’（Ｒ’为炔基或烯基）的研究尚未见文献报道。我们以三苄基氯化锡和炔基（烯基）膦酸单钠为原料,合成了６种三苄基锡（ＩＶ）炔基（烯基）膦酸类化合物。并用元素分析、红外光谱、核磁共振、氢谱和锡谱、质谱及热重分析等手段表征了这些化合…     

三苄基锡(IV)炔基(烯基)膦酸衍生物的合成及结构表征

Six novel tribenzyltin(IV) dervatives of alkynyl or alkenyl Phosphonic acid (PhCH₂)₃SnOP(O)(OH)R, Where R=C≡CPh, C≡CC₃H₇ n,C≡CC₄H₉ n, C≡CC₅H₁₁ n,C≡CC₆H₁₃ n, CH=CClPh,were synthesized by resaction of the monosodium salt of the alkynyl or alkenyl phosphonic acid with tribenzyltin(IV) chloride in benzene. Their structures were cheracterized by elementary analysis, IR,¹H NMR, ¹¹⁹Sn NMR, MS and TG DTA. The results showed that these compounds arefive coordinated -O-P-O-bridged polymers.     

三溴化金催化端炔与二芳基二硒醚反应合成炔基硒醚

炔基硒醚是合成一些有机硒化合物的重要起始物。本文研究发现,在三溴化金(Au Br3)催化下,端位炔和二芳基二硒醚在弱碱(如碳酸钾)存在下反应,生成炔基芳基硒醚,产率为69%~98%;在空气参与下,于80℃下进行反应,反应条件简单,且二硒醚的两个硒原子均可以被利用。二甲基亚砜(DMSO)是合适的溶剂,在极性较小的溶剂(如甲苯、四氢呋喃)中,此反应不能进行。芳基炔(如苯乙炔、对甲基苯乙炔、对氯苯乙炔等)、烯基炔(如环己烯乙炔)和烷基炔(如1-壬炔)均能顺利进行此反应。当芳基炔苯环的间位或邻位连有取代基时,反应产率较低(69%~82%),而对位无论是连有吸电子基还是给电子基,该反应均可以得到很高的产率(95%)。     

Synthesis and Diversification of Macrocyclic Alkynediyl Sulfide Peptides

The synthesis of rare macrocyclic alkynediyl sulfides by a Cu-catalyzed C_sp−S cross-coupling is presented. The catalytic protocol (Cu(MeCN)₄PF₆/dtbbpy) promotes macrocyclization of peptides, dipeptides and tripeptides at ambient temperature (14 examples, 23→73 % yields) via thiols and bromoalkynes, and is chemoselective with regards to terminal alkynes. Importantly, the underexplored alkynediyl sulfide functionality incorporates a rigidifying structural element and opens new opportunities for diversification of macrocyclic frameworks through S oxidation, halide addition and azide–alkyne cycloaddition chemistries to integrate sulfones, halides or valuable fluorophores (7 examples, 37→92 % yields).     

Pd‐NHC‐Catalyzed Alkynylation of General Aryl Sulfides with Alkynyl Grignard Reagents

Cross‐coupling reactions of unactivated aryl sulfides with alkynylmagnesium chloride have been invented to afford 1‐aryl‐1‐alkynes with the aid of a palladium/N‐heterocyclic carbene complex. This reaction has by far the widest scope of all transformations utilizing aryl sulfides and alkynes, while known cross‐coupling alkynylations of aryl‐sulfur electrophiles require activated azaaryl sulfides, thiolactams, or arenesulfonyl chlorides. The alkynylation of aryl sulfides is compatible with typical protecting functional groups. The alkynylation is applied to the synthesis of benzofuran‐based fluorescent molecules by taking advantage of characteristic organosulfur chemistry.     

由硫醚或亚砜氧化制砜的研究进展

对氧化硫醚或亚砜成为砜的方法作一评述,参考文献50篇.     

Synthesis and Characterization of Alkynyl Complexes of Groups 1 and 2

The synthesis of N‐heterocyclic carbene adducts of alkynyl lithium and magnesium is achieved, and different degrees of association are observed. Reaction of strontium amide nacnacSrN(SiMe₃)₂(thf) (nacnac=CH(CMe2,6‐iPr₂C₆H₃N)₂) with PhC≡CH in THF yields the dimeric alkynyl complex [nacnacSr(thf)(μ‐C≡CPh)]₂ which shows an interesting coordination geometry around the metal center. The compound retains the THF molecules, unlike its lighter congener, even in hydrocarbon solvents.     

Synthesis of Dibenzothiophenes by Pd‐Catalyzed Dual CH Activation from Diaryl Sulfides

Palladium‐catalyzed dual C?H functionalization of diaryl sulfides to form dibenzothiophenes (DBTs) by oxidative dehydrogenative cyclization is reported. This protocol afforded various DBTs in moderate to good yields with tolerance of a wide variety of substrates. Benzo[1,2‐b:4,5‐b′]bis[b]benzothiophene was successfully synthesized by this method, which was used as an organic semiconductor for field‐effect transistors.     

Facile Preparation of Aryl Sulfides Catalyzed by PEG400 and Nickel without Solvent

A variety of aryl sulfides were synthesized by aryl bromides with thiols, with PEG400 and nickel as catalysts under basic conditions in the absence of solvents. This article reported an easy and convenient method for formation of aryl‐sulfur bonds.     

Synthesis and Properties of β-Oxo Sulfides of the Dioxothiolane Series

It was shown that the hydroxy group in β-hydroxy sulfides of the dioxothiolane series can be oxidized selectively to a carbonyl group in the presence of a sulfide group. A sequence of transformations leading to the final β-oxo sulfides was proposed and was confirmed experimentally. A new original method was developed for the production of β-oxo sulfides. Some characteristics of the synthesized compounds were studied. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 974–985, July, 2005.     

Synthesis of Unsymmetrical Sulfides Derived from Tetrazole-5-thiols

A series of unsymmetrical sulfides derived from 1-substituted tetrazole-5-thiols was prepared by fusion of the corresponding 1-R-tetrazole-5-thiol sodium salt with 1-R'-5-halotetrazole. The structure was confirmed by ¹H NMR and ¹³C NMR spectra. The target compounds were prepared in 50-80% yields.     

Facile Method for One-Step Synthesis of 2,4,5-Triarylimidazoles Under Catalyst-Free,Solvent-Free,and Microwave-Irradiation Conditions

A green and efficient method for the synthesis of 2,4,5-triarylimidazoles by one-step condensation reaction of benzil, aromatic aldehyde, and ammonium acetate under catalyst-free, solvent-free, and microwave-irradiation conditions is reported. This method had many dramatic advantages, such as the short reaction time (3–5 min), good yields (80–99%), environmental friendliness, and convenient operation.