cas 5296-64-0, ALLYL PHENYL SULFIDE | Articles data

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Size-dependent oxidation of monodisperse silicon nanocrystals with allylphenylsulfide surfaces
The synthesis and characterization of size-separated silicon nanocrystals functionalized with a heteroatom-substituted organic capping group, allylphenylsulfide, via photochemical hydrosilylation are described for the first time. These silicon nanocrystals form colloidally stable and highly photoluminescent dispersions in nonpolar organic solvents with an absolute quantum yield as high as 52% which is 20% above that of the allylbenzene analogue. Solutions of the size-separated fractions are characterized over time to monitor the effect of aging in air by following the change of their photoluminescence and absolute quantum yields, supplemented by transmission electron microscopy.
Rinck, Julia,Schray, Dirk,Kübel, Christian,Powell, Annie K.,Ozin, Geoffrey A.
p. 335 - 340
(2015)
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Synthesis of sulfimides and N-Allyl-N-(thio)amides by Ru(II)catalyzed nitrene transfer reactions of N-acyloxyamides
The N-acyloxyamides were employed as effective N-acyl nitrene precursors in reactions with thioethers under the catalysis of a commercially available Ru(II) complex, from which a variety of sulfimides were synthesized efficiently and mildly. If an allyl group is contained in the thioether precursor, the [2,3]-sigmatropic rearrangement of the sulfimide occurs simultaneously and the N-allyl-N-(thio)amides were obtained as the final products. Preliminary mechanistic studies indicated that the Ru-nitrenoid species should be a key intermediate in the transformation.
Zhang, Xinyu,Lin, Bo,Chen, Jianhui,Chen, Jiajia,Luo, Yanshu,Xia, Yuanzhi
supporting information
p. 819 - 825
(2021/02/01)

Iron(II) and Copper(I) Control the Total Regioselectivity in the Hydrobromination of Alkenes
A new method that allows the complete control of the regioselectivity of the hydrobromination reaction of alkenes is described. Herein, we report a radical procedure with TMSBr and oxygen as common reagents, where the formation of the anti-Markovnikov product occurs in the presence of parts per million amounts of the Cu(I) species and the formation of the Markovnikov product occurs in the presence of 30 mol % iron(II) bromide. Density functional theory calculations combined with Fukui's radical susceptibilities support the obtained results.
Cruz, Daniel A.,Sinka, Victoria,De Armas, Pedro,Steingruber, Hugo Sebastian,Fernández, Israel,Martín, Víctor S.,Miranda, Pedro O.,Padrón, Juan I.
supporting information
p. 6105 - 6109
(2021/08/18)

Yb(iii)-catalysedsyn-thioallylation of ynamides
Reported herein is asyn-thioallylation of ynamides incorporating a sulfide moiety at the α-position and an allyl group at the β-position of the ynamide. The transformation is successful under ytterbium(iii)-catalysis, providing access to highly substituted thioamino-skipped-dienes with broad substrate scope. Thus, tetrasubstituted olefins (with four different functional groups: amide, phenyl, thioaryl/alkyl, and allyl on the carbon centers) are made in a single step from readily accessible ynamides, preserving complete atom economy. The reaction can be extended to the synthesis of selenoamino dienes by ynamidesyn-selenoallylation. DFT studies and control experiments provide insight into the reaction mechanism.
Dutta, Shubham,Gandon, Vincent,Gogoi, Manash Protim,Mallick, Rajendra K.,Prabagar, B.,Sahoo, Akhila K.,Vanjari, Rajeshwer,Yang, Shengwen
supporting information
p. 7521 - 7524
(2021/08/05)

A mild and chemoselective CALB biocatalysed synthesis of sulfoxides exploiting the dual role of AcOEt as solvent and reagent
A mild, chemoselective and sustainable biocatalysed synthesis of sulfoxides has been developed exploiting CALB and using AcOEt with a dual role of more environmentally friendly reaction solvent and enzyme substrate. A series of sulfoxides, including the drug omeprazole, have been synthesised in high yields and with excellent E-factors.
Anselmi, Silvia,Liu, Siyu,Kim, Seong-Heun,Barry, Sarah M.,Moody, Thomas S.,Castagnolo, Daniele
supporting information
p. 156 - 161
(2021/01/14)

Electrophilic Chlorine from Chlorosulfonium Salts: A Highly Chemoselective Reduction of Sulfoxides
Herein, we describe a selective late-stage deoxygenation of sulfoxides based on a novel application of chlorosulfonium salts and demonstrate a new process using these species generated in situ from sulfoxides as the source of electrophilic chlorine. The use of highly nucleophilic 1,3,5-trimethoxybenzene (TMB) as the reducing agent is described for the first time and applied in the deoxygenation of simple and functionalized sulfoxides. The method is easy to handle, economic, suitable for gram-scale operations, and readily applied for poly-functionalized molecules, as demonstrated with more than 45 examples, including commercial medicines and analogues. We also report the results of competition experiments that define the more reactive sulfoxide and we present a mechanistic proposal based on substrate and product observations.
Acosta-Guzmán, Paola,Mahecha-Mahecha, Camilo,Gamba-Sánchez, Diego
supporting information
p. 10348 - 10354
(2020/07/13)

Nickel phosphide nanoalloy catalyst for the selective deoxygenation of sulfoxides to sulfides under ambient H2pressure
Exploring novel catalysis by less common, metal-non-metal nanoalloys is of great interest in organic synthesis. We herein report a titanium-dioxide-supported nickel phosphide nanoalloy (nano-Ni2P/TiO2) that exhibits high catalytic activity for the deoxygenation of sulfoxides. nano-Ni2P/TiO2 deoxygenated various sulfoxides to sulfides under 1 bar of H2, representing the first non-noble metal catalyst for sulfoxide deoxygenation under ambient H2 pressure. Spectroscopic analyses revealed that this high activity is due to cooperative catalysis by nano-Ni2P and TiO2. This journal is
Fujita, Shu,Mitsudome, Takato,Mizugaki, Tomoo,Yamaguchi, Sho,Yamasaki, Jun,Yamazoe, Seiji
supporting information
p. 8827 - 8833
(2020/11/23)

Air-stable binuclear Titanium(IV) salophen perfluorobutanesulfonate with zinc power catalytic system and its application to C–S and C–Se bond formation
An air-stable μ-oxo-bridged binuclear Lewis acid of titanium(IV) salophen perfluorobutanesulfonate [{Ti(salophen)H2O}2O][OSO2C4F9]2 (1) was successfully synthesized by the reaction of TiIV(salophen)Cl2 with AgOSO2C4F9 and characterized by techniques such as IR, NMR and HRMS. This complex was stable open to air over a year, and exhibited good thermal stability and high solubility in polar organic solvents. The complex also had relatively strong acidity with a strength of 0.8 Ho ≤ 3.3, and showed high catalytic efficiency towards various C–S and C–Se bond formations in the presence of zinc power. This catalytic system affords a mild and efficient approach to synthesis of thio- and selenoesters, α-arylthio- and seleno-carbonyl compounds, and thio- and selenoethers.
Wang, Lingxiao,Qiao, Jie,Wei, Jiancong,Liang, Zhiwu,Xu, Xinhua,Li, Ningbo
(2020/01/08)

One-pot Synthesis of Allyl Sulfides from Sulfinate Esters and Allylsilanes through Reduction of Alkoxysulfonium Intermediates
An efficient method to synthesize allyl sulfides from sulfinate esters and allylsilanes is described. Based on the reactivity of isolated allyl(methoxy)phenyl sulfonium triflate, we have developed a simple one-pot method for the allyl sulfide synthesis by S-allylation of sulfinate esters and subsequent reduction with sodium borohydride. A number of allyl sulfides were prepared by this method leaving various functional groups unreacted.
Hosoya, Takamitsu,Kobayashi, Akihiro,Matsuzawa, Tsubasa,Yoshida, Suguru
supporting information
p. 813 - 816
(2020/07/23)

Exploiting the radical reactivity of diazaphosphinanes in hydrodehalogenations and cascade cyclizations
The remarkable reducibility of diazaphosphinanes has been extensively applied in various hydrogenations, based on and yet limited by their well-known hydridic reactivity. Here we exploited their unprecedented radical reactivity to implement hydrodehalogenations and cascade cyclizations originally inaccessible by hydride transfer. These reactions feature a broad substrate scope, high efficiency and simplicity of manipulation. Mechanistic studies suggested a radical chain process in which a phosphinyl radical is generated in a catalytic cycle via hydrogen-atom transfer from diazaphosphinanes. The radical reactivity of diazaphosphinanes disclosed here differs from their well-established hydridic reactivity, and hence, opens a new avenue for diazaphosphinane applications in organic syntheses.
Cheng, Jin-Pei,Yang, Jin-Dong,Zhang, Jingjing
p. 4786 - 4790
(2020/06/18)

Sulfoxide synthesis from sulfinate esters under Pummerer-like conditions
A facile synthetic method for the preparation of allyl sulfoxides byS-allylation of sulfinate esters proceeds through sulfonium intermediates without [3,3]-sigmatropic rearrangement and further Pummerer-type reactions of the resulting allyl sulfoxides. On the basis of the plausible reaction mechanism involving sulfonium salt intermediates,S-alkynylation andS-arylation were also accomplished.
Kobayashi, Akihiro,Matsuzawa, Tsubasa,Hosoya, Takamitsu,Yoshida, Suguru
p. 5429 - 5432
(2020/06/04)

Design, Multigram Synthesis, and in Vitro and in Vivo Evaluation of Propylamycin: A Semisynthetic 4,5-Deoxystreptamine Class Aminoglycoside for the Treatment of Drug-Resistant Enterobacteriaceae and Other Gram-Negative Pathogens
Infectious diseases due to multidrug-resistant pathogens, particularly carbapenem-resistant Enterobacteriaceae (CREs), present a major and growing threat to human health and society, providing an urgent need for the development of improved potent antibiotics for their treatment. We describe the design and development of a new class of aminoglycoside antibiotics culminating in the discovery of propylamycin. Propylamycin is a 4′-deoxy-4′-alkyl paromomycin whose alkyl substituent conveys excellent activity against a broad spectrum of ESKAPE pathogens and other Gram-negative infections, including CREs, in the presence of numerous common resistance determinants, be they aminoglycoside modifying enzymes or rRNA methyl transferases. Importantly, propylamycin is demonstrated not to be susceptible to the action of the ArmA resistance determinant whose presence severely compromises the action of plazomicin and all other 4,6-disubstituted 2-deoxystreptamine aminoglycosides. The lack of susceptibility to ArmA, which is frequently encoded on the same plasmid as carbapenemase genes, ensures that propylamycin will not suffer from problems of cross-resistance when used in combination with carbapenems. Cell-free translation assays, quantitative ribosome footprinting, and X-ray crystallography support a model in which propylamycin functions by interference with bacterial protein synthesis. Cell-free translation assays with humanized bacterial ribosomes were used to optimize the selectivity of propylamycin, resulting in reduced ototoxicity in guinea pigs. In mouse thigh and septicemia models of Escherichia coli, propylamycin shows excellent efficacy, which is better than paromomycin. Overall, a simple novel deoxy alkyl modification of a readily available aminoglycoside antibiotic increases the inherent antibacterial activity, effectively combats multiple mechanisms of aminoglycoside resistance, and minimizes one of the major side effects of aminoglycoside therapy.
Matsushita, Takahiko,Sati, Girish C.,Kondasinghe, Nuwan,Pirrone, Michael G.,Kato, Takayuki,Waduge, Prabuddha,Kumar, Harshitha Santhosh,Sanchon, Adrian Cortes,Dobosz-Bartoszek, Malgorzata,Shcherbakov, Dimitri,Juhas, Mario,Hobbie, Sven N.,Schrepfer, Thomas,Chow, Christine S.,Polikanov, Yury S.,Schacht, Jochen,Vasella, Andrea,B?ttger, Erik C.,Crich, David
supporting information
p. 5051 - 5061
(2019/03/26)

Intermolecular Aminoallylation of Alkenes Using Allyl-Oxyphthalimide Derivatives: A Case Study in Radical Polarity Effects
A case study on the polarity effects of radical mediated intermolecular alkene aminoallylation is presented herein. This radical group transfer method pairs vinyl ethers with electronically deficient allyl-oxyphthalimide derivatives to give difunctionalized products while illustrating the guiding effects of polarity on this radical reactivity.
Lardy, Samuel W.,Schmidt, Valerie A.
supporting information
p. 6796 - 6799
(2019/11/03)

Synthesis and nano-Pd catalyzed chemoselective oxidation of symmetrical and unsymmetrical sulfides
A highly chemoselective, efficient and nano-Pd catalyzed protocol for the rapid construction of sulfoxides and sulfones via the oxidation of symmetrical and unsymmetrical sulfides using H2O2 as an oxidant has been developed, respectively. The ready availability of starting materials, easy recovery and reutilization of the catalyst, wide substrate scope, and high yields make this protocol an attractive alternative. The process also involves the metal-free and microwave-promoted synthesis of symmetrical diarylsulfides, and FeCl3-mediated preparation of symmetrical diaryldisulfides through the reaction of arenediazonium tetrafluoroborates with Na2S·9H2O as a sulfur source. In addition, unsymmetrical sulfides were generated via the K2CO3-mediated reaction of arenediazonium tetrafluoroborates with symmetrical disulfides.
Li, Xing,Du, Jia,Zhang, Yongli,Chang, Honghong,Gao, Wenchao,Wei, Wenlong
p. 3048 - 3055
(2019/03/21)

Organic oxidations promoted in vortex driven thin films under continuous flow
With increasing concerns for the environmental impact of chemical manufacturing, reagents and processes that align with the principles of green chemistry are essential. The fundamental oxidation of organic substrates is no exception and in this report three distinct modes of green oxidation are demonstrated in a vortex fluidic device (VFD) under continuous flow: aerobic oxidation, oxidation using chlorine bleach, and oxidation using hydrogen peroxide. The VFD, which is a thin film microfluidic platform, revealed clear advantages in these oxidations in comparison to traditional batch reactor processing: Efficient mass transfer of gases in the dynamic thin film increased the rate of aerobic oxidations, and the intense micromixing allowed multi-phase oxidations to proceed efficiently, obviating the need for organic solvents and phase transfer catalysts. In addition, the rapid dissipation of heat in the VFD also improved the safety profile and stereoselectivity for exothermic oxidations.
Pye, Scott J.,Dalgarno, Scott J.,Chalker, Justin M.,Raston, Colin L.
supporting information
p. 118 - 124
(2018/01/17)

Preparation method and application of novel ionic binuclear Schiff base titanium complex
The invention provides a preparation method of a novel ionic binuclear Schiff base titanium complex and a synthetic method of applying the novel ionic binuclear Schiff base titanium complex to catalyze zinc powder and reduce disulfide or selenide to prepare sulfo(seleno) ester and dissymmetric sulfoether(selenide). The complex is a cationic binuclear Schiff base titanium complex, wherein titaniumatoms are bridged by oxygen atoms and are coordinated with a Schiff base ligand and a hydrone, and an ionic bond is formed by a cation part and an anion part of whole Schiff base titanium. The ionic binuclear Schiff base titanium complex is used as a catalyst, the zinc powder is used as a reducer, the disulfide(selenide) can be reduced and fractured, and the disulfide(selenide) can further and respectively react with anhydride, an alpha-bromo carbonyl compound and bromoalkane to prepare the sulfo(seleno) ester and the dissymmetric sulfoether(selenide). According to the preparation method provided by the invention, the defects that traditional lewis acid halide is deliquescent, an absolute solvent is used, conditions are strict and the like are overcome; an effective path for reducing the disulfide or selenide to prepare the sulfo(seleno) ester and the dissymmetric sulfoether(selenide) is provided, and the preparation method has the advantages of high yield, simpleness in operation andthe like.
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Paragraph 0092; 0093

(2018/04/03)

Selective Oxidation of Sulfides in Flow Chemistry
A packed-bed reactor with oxone has been employed for selective oxidations of sulfur compounds. Various sulfides containing different functional groups are efficiently oxidized to the corresponding sulfoxides without formation of sulfones or other side products.
Silva, Filipa,Baker, Alastair,Stansall, James,Michalska, Weronika,Yusubov, Mehkman S.,Graz, Michael,Saunders, Robert,Evans, Gareth J. S.,Wirth, Thomas
p. 2134 - 2137
(2018/05/31)

One-pot synthesis of α-phenylsulfinyl ketones by reaction of phenyl benzenethiosulfinate with enolate anions, and synthesis of sulfoxides and sulfides by its reaction with Grignard reagents
Phenyl benzenethiosulfinate reacts with enolate anions derived from ketones to give α-phenylsulfinyl ketones directly, together with minor amounts of α-phenylsulfanyl ketones. These are easily separated by forming the water-soluble sodium salts of the sulfinyl compounds. Grignard reagents also react with phenyl benzenethiosulfinate, to give mixtures of sulfoxides and sulfides.
Fakhry, Jerome,Grayson, David H.
p. 556 - 563
(2017/12/28)

Aqueous hemin catalyzed sulfonium ylide formation and subsequent [2,3]-sigmatropic rearrangements
A mild hemin catalytic system for sulfonium ylide generation via a metal carbenoid and a subsequent [2,3]-sigmatropic rearrangement reaction in aqueous solvent is well-established, with the assistance of cyclodextrin (CD) and Triton X-100. The protocol displays high catalytic activity with a broad substrate scope of aryl/alkyl allyl sulfides and diazo reagents, affording homoallyl sulfide products in up to 99% yield. Notably, this catalytic system is successful for water-insoluble allyl sulfides but ineffective for allyl amines or allyl ethers. Moreover, an unprecedented cascade reaction of sulfonium ylide formation, [2,3]-sigmatropic rearrangement and C-H insertion was reported.
Xu, Xiaofei,Li, Chang,Tao, Zhihao,Pan, Yuanjiang
supporting information
p. 1245 - 1249
(2017/08/15)

Investigations on Gold-Catalyzed Thioalkyne Activation Toward Facile Synthesis of Ketene Dithioacetals
Nucleophilic addition to thioalkynes was investigated under various catalytic conditions with gold(I) complexes being identified as the optimal catalysts. Structural evaluation of the product revealed an unexpected cis-addition, arising from a gold-associated thioketene intermediate. Based on this interesting mechanistic insight, a gold(I)-catalyzed thioether addition to thioalkynes was developed as a novel approach to prepare ketene dithioacetals with good yields and high efficiency.
Ye, Xiaohan,Wang, Jin,Ding, Shengtao,Hosseyni, Seyedmorteza,Wojtas, Lukasz,Akhmedov, Novruz G.,Shi, Xiaodong
supporting information
p. 10506 - 10510
(2017/08/09)

Regioselective Alkoxycarbonylation of Allyl Phenyl Ethers Catalyzed by Pd/dppb under Syngas Conditions
A simple and regioselective synthesis of phenoxy esters and phenylthio esters is reported. The products are obtained by selective alkoxycarbonylation catalyzed by Pd2(dba)3, 1,4-bis(diphenylphisphino)butane (dppb), and syngas (CO/H2) in chloroform/alcohol. This methodology affords bifunctional products in good yield with excellent n-selectivity and without the need to use additives.
Amézquita-Valencia, Manuel,Alper, Howard
p. 3860 - 3867
(2016/05/24)

Bi(OTf)3-Catalysed Access to 2,3-Substituted Isoindolinones and Tricyclic N,O-Acetals by Trapping of Bis-N-Acyliminium Species in a Tandem Process
New 1,3-bis-N-acyliminium species generated easily with nontoxic Bi(OTf)3catalyst at very low loadings (2 mol-%) were trapped inter- and intramolecularly with various poly-nucleophiles. This mild, efficient, practical and general tandem approach provides an array of substituted isoindolinones and cyclic N,O-acetals.
Aliyenne, Ahmed,Pin, Frédéric,Nimbarte, Vijaykumar D.,Lawson, Ata Martin,Comesse, Sébastien,Sanselme, Morgane,Tognetti, Vincent,Joubert, Laurent,Da?ch, Adam
p. 3592 - 3602
(2016/07/28)

Method of manufacturing compds. Allylnaphthol
PROBLEM TO BE SOLVED: To provide a production method of an allyl compound of carrying out the dehydration allylation of a substrate having S, C or N which is a nucleophilic atom, especially S under the presence of a catalyst system consisting of a catalyst precursor having a specific structure and a specific ligand. SOLUTION: The production method of allyl compounds comprises as follow. A catalyst precursor chosen from Formula (1) and Formula (2) and a ligand are mixed, or a catalyst precursor, an allyl alcohol, and a ligand are mixed, then allyl alcohols and a substrate are blended and made to react. The ligand is quinaldic acid or picolinic acid, and the substrate is thiols, thiocarboxylic acids or the like. [Ru(C5H5)(CH3CN)3]PF6(1). [Ru[C5(CH3)5](CH3CN)3]PF6(2). COPYRIGHT: (C)2012,JPOandINPIT
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Paragraph 0030-0032; 0050; 0062

(2018/06/26)

Efficient Oxidation of Sulfides to Sulfoxides and Deoxygenation of Sulfoxides over Carbonaceous Solid Acid
Carbonaceous Solid Acid (CSA) was found to be a highly efficient, environmentally friendly, recyclable heterogeneous solid acid for the oxidation of sulfides and deoxygenation of sulfoxides, in good to excellent yields under mild reaction conditions.
Atabaki, Fariborz,Abedini, Ebrahim,Shokrolahi, Arash
p. 1169 - 1176
(2015/08/04)

Allyl sulphides in olefin metathesis: Catalyst considerations and traceless promotion of ring-closing metathesis
Allyl sulphides are reactive substrates in ruthenium-catalysed olefin metathesis reactions, provided each substrate is matched with a suitable catalyst. A profile of catalyst activity is described, along with the first demonstration of allyl sulphides as traceless promoters in relayed ring-closing metathesis reactions. This journal is
Edwards, Grant A.,Culp, Phillip A.,Chalker, Justin M.
supporting information
p. 515 - 518
(2015/02/19)

Expanding the horizon of intermolecular trapping of in situ generated α-oxo gold carbenes: Efficient oxidative union of allylic sulfides and terminal alkynes via C-C bond formation
With a new P,S-bidentate phosphine as the ligand to gold(i), the α-oxo gold carbenes generated in situ via gold-catalyzed intermolecular oxidation of terminal alkynes were effectively trapped by various allylic sulfides, resulting in the formation of α-aryl(alkyl)thio-γ,δ- unsaturated ketones upon facile [2,3]sigmatropic rearrangements. This journal is the Partner Organisations 2014.
Li, Jiabin,Ji, Kegong,Zheng, Renhua,Nelson, Jonathan,Zhang, Liming
supporting information
p. 4130 - 4133
(2014/04/03)

Dynamic kinetic resolution of allylic sulfoxides by Rh-catalyzed hydrogenation: A combined theoretical and experimental mechanistic study
A dynamic kinetic resolution (DKR) of allylic sulfoxides has been demonstrated by combining the Mislow [2,3]-sigmatropic rearrangement with catalytic asymmetric hydrogenation. The efficiency of our DKR was optimized by using low pressures of hydrogen gas to decrease the rate of hydrogenation relative to the rate of sigmatropic rearrangement. Kinetic studies reveal that the rhodium complex acts as a dual-role catalyst and accelerates the substrate racemization while catalyzing olefin hydrogenation. Scrambling experiments and theoretical modeling support a novel mode of sulfoxide racemization which occurs via a rhodium π-allyl intermediate in polar solvents. In nonpolar solvents, however, the substrate racemization is primarily uncatalyzed. Computational studies suggest that the sulfoxide binds to rhodium via O-coordination throughout the catalytic cycle for hydrogenation.
Dornan, Peter K.,Kou, Kevin G. M.,Houk,Dong, Vy M.
supporting information
p. 291 - 298
(2014/01/23)

Nickel-Schiff base complex catalyzed C-S cross-coupling of thiols with organic chlorides
We report an efficient, mild and convenient synthetic protocol for the C-S cross-coupling reaction of various aryl, benzyl, allyl chlorides and thiols using 5 mol % Nickel-Schiff base catalyst with NaOH as the base, in DMF at 70 °C. Using this protocol, we have shown that a variety of aryl sulfides can be synthesized in excellent yields from readily available organic chlorides and thiols.
Gogoi, Prasanta,Hazarika, Sukanya,Sarma, Manas J.,Sarma, Kuladip,Barman, Pranjit
p. 7484 - 7489
(2014/12/10)

Gas-phase S-alkylation of benzenethiol with aliphatic alcohols, ethers, esters, alkyl halides and olefins over halide cluster catalysts of Groups 5 and 6 transition metals
Benzenethiol was reacted with methanol under a hydrogen stream over [(Nb6Cl12)Cl2(H2O) 4]·6H2O supported on silica gel. Catalytic activity of the cluster commenced above 250 °C, yielding methyl phenyl sulfide. The selectivity was 98% at 400 °C. Molybdenum, tantalum and tungsten halide clusters with the same octahedral metal framework also catalyzed the reaction. Primary alcohols with shorter alkyl chains were effective reagents for the S-alkylation. Aliphatic ethers, dialkyl carbonates, orthoesters and alkyl halides were effective reagents for the S-alkylation. When 1-hexene was applied to the reaction, spontaneous and catalytic S-alkylation proceeded simultaneously above 200 °C, yielding n-hexyl phenyl sulfide. When alkyl acetates were subjected to this reaction, the niobium cluster afforded S-phenyl thioacetate, and the other clusters afforded alkyl phenyl sulfides selectively. A Br?nsted acid site attributable to a hydroxo ligand, which is formed on the cluster complex by thermal activation, is proposed as the active site of the catalysts.
Nagashima, Sayoko,Kudo, Kentaro,Yamazaki, Hitomi,Kamiguchi, Satoshi,Chihara, Teiji
p. 50 - 56
(2013/02/25)

NaI/silica sulfuric acid as an efficient reducing system for deoxygenation of sulfoxides in poly ethylene glycol (PEG-200)
Deoxygenation of structurally diverse sulfoxides including dialkyl, diaryl, aryl alkyl and allyl sulfoxides to the corresponding sulfides were carried out using a NaI/silica sulfuric acid reducing system at room temperature in poly ethylene glycol (PEG-200) in excellent yields.
Zarei, Morteza,Ameri, Mohammad Aghil,Jamaleddini, Azar
p. 259 - 263
(2013/08/26)

Ionic liquid/PPh3 promoted cleavage of diphenyl disulfide and diselenide: A straight-forward metal-free one-pot route to the synthesis of unsymmetrical sulfides and selenides
A metal-free cleavage of diphenyl disulfide and diphenyl diselenide has been achieved using ionic liquid/triphenyl phosphine (PPh3) and a convenient protocol for the one-pot synthesis of unsymmetrical sulfides and selenides by condensing 'in situ' generated thiolate or selenate anion with alkyl halides has been developed. In addition, 1,4-conjugate addition of the generated thiolate anions to activated alkenes has also been demonstrated. The ionic liquid, 1-methyl-3-pentyl imidazolium bromide, [pmIm]Br plays a crucial role in promoting the course of the reactions and shows superior activity and selectivity compared to other solvents. The [pmIm]Br has been reused for at least five times without appreciable loss of activity.
Banerjee, Subhash,Adak, Laksmikanta,Ranu, Brindaban C.
supporting information; experimental part
p. 2149 - 2152
(2012/05/05)

Highly chemoselective synthesis of aryl allylic sulfoxides through calcium hypobromite oxidation of aryl allylic sulfides
A highly chemoselective oxidation of widely substituted aryl allylic sulfides, prepared by allylation of arylthioethers with KF-Celite, to the corresponding aryl allylic sulfoxide was achieved by employing calcium hypobromite. Neither over-oxidation to sulfones nor halogenation of the aromatic rings was observed. The protocol may be successfully applied for the oxidation of substituted allylic systems (i.e., 2-haloallyl) that per se could interact with the oxidizing agent.
Pace, Vittorio,Castoldi, Laura,Holzer, Wolfgang
supporting information; experimental part
p. 967 - 972
(2012/03/11)

Catalytic activation of diazo compounds using electron-rich, defined iron complexes for carbene-transfer reactions
Carbene transfer: The electron-rich iron complex Bu4N[Fe(CO) 3(NO)] efficiently catalyzes different carbene-transfer reactions. Various diazo compounds can be used. The high stability of the employed iron complexes is demonstrated by the generation of the diazo reagent in situ and a sequential iron-catalyzed allylic sulfenylation/Doyle-Kirmse reaction. Copyright
Holzwarth, Michael S.,Alt, Isabel,Plietker, Bernd
supporting information; experimental part
p. 5351 - 5354
(2012/07/14)

Rh(II)-catalyzed [2,3]-sigmatropic rearrangement of sulfur ylides derived from N-tosylhydrazones and sulfides
In this paper, Rh2(OAc)4-catalyzed [2,3]-sigmatropic rearrangement of sulfur ylides derived from N-tosylhydrazones and sulfides is reported. A series of tosylhydrazones derived from aldehydes were successfully used for [2,3]-sigmatropic rearrangement by reaction with either allylic phenyl sulfides or propargyl phenyl sulfides. The reaction conditions were optimized and afforded the products in moderate to good yields. In addition, a novel and convenient approach for the synthesis of cyclobutenones and cyclopropanes has been developed through direct oxidation of the rearrangement products.
Li, Yuye,Huang, Zhongxing,Wu, Xinhu,Xu, Peng-Fei,Jin, Jing,Zhang, Yan,Wang, Jianbo
experimental part
p. 5234 - 5240
(2012/08/07)

Catalyst-free imidation of allyl sulfides with chloramine-T and subsequent [2,3]-sigmatropic rearrangement
A facile synthesis of various allyl sulfonamides based on imidation of allyl sulfides with chloramine-T and subsequent [2,3]-sigmatropic rearrangement has been achieved without metal catalysts. The reaction completes smoothly within 10 min, providing excellent yields in environment friendly solvent of alcohol. Functional groups such as bromine, hydroxyl, protected amido and aldehyde are tolerant under this condition.
Jiang, Yubo,Mo, Fanyang,Qiu, Di,Kuang, Chunxiang,Zhang, Yan,Wang, Jianbo
p. 2029 - 2035
(2012/11/07)

Synthesis of a wide range of thioethers by indium triiodide catalyzed direct coupling between alkyl acetates and thiosilanes
An indium triiodide-catalyzed substitution of the acetoxy group in alkyl acetates with thiosilanes provides access to a variety of thioethers. The method is efficient for a wide scope of acetates such as primary alkyl, secondary alkyl, tertiary alkyl, allylic, benzylic, and propargylic acetates.
Nishimoto, Yoshihiro,Okita, Aya,Yasuda, Makoto,Baba, Akio
supporting information; experimental part
p. 1846 - 1849
(2012/06/18)

Zn in ionic liquid: An efficient reaction media for the synthesis of diorganyl chalcogenides and chalcogenoesters
A straightforward and efficient methodology is described to synthesize structurally diverse diorganyl selenides, sulfides, seleno- and thioesters by using commercially available Zn dust in ionic liquid. Excellent yields were achieved under neutral conditions at room temperature in a short time. The solvent/ionic liquid is reusable and exhibited higher performance as compared with organic solvents.
Narayanaperumal, Senthil,Alberto, Eduardo E.,Gul, Kashif,Kawasoko, Cristiane Yuriko,Dornelles, Luciano,Rodrigues, Oscar E.D.,Braga, Antonio Luiz
experimental part
p. 4723 - 4730
(2011/06/27)

Bimetallic system for the synthesis of diorganyl selenides and sulfides, chiral β-seleno amines, and seleno- and thioesters
The bimetallic reagent Sn(II)/Cu(II) in [bmim]BF4 was efficiently used for the cleavage of diaryl diselenides and disulfides and reacts with a variety of organic substrates, such as organic halides, acid chlorides, and β-amino mesylates affording the diorganyl selenides and sulfides within very short reaction times, under mild conditions and with excellent yields, using BMIM-BF4 as a reusable solvent.
Gul, Kashif,Narayanaperumal, Senthil,Dornelles, Luciano,Rodrigues, Oscar E.D.,Braga, Antonio Luiz
supporting information; experimental part
p. 3592 - 3596
(2011/07/31)

One-pot reductive sulfenylation and thiocyanation of carbonyl compounds in ionic liquid media
The first example of an efficient one-pot reductive sulfenylation and thiocyanation of carbonyl compounds in environmentally benign ionic liquid (IL) media is reported. The process involves reduction of carbonyl compounds with NaBH4 in the IL [bmim]BF4 followed by I2-catalyzed reaction of the resulting alcohols with aromatic/aliphatic thiols or ammonium thiocyanate in the same vessel to afford sulfides or thiocyanates, respectively, in excellent yields (78-93%). Notably, the protocol precludes the necessity to prepare and isolate the intermediate alcohols in a separate step as they are formed in situ, and the IL used can be recycled easily for further use without any loss of efficiency. Copyright
Yadav, Lal Dhar S.,Garima,Kapoor, Ritu
experimental part
p. 100 - 112
(2011/03/17)

Scope of the allylation reaction with [RuCp(PP)]+ catalysts: Changing the nucleophile or allylic alcohol
The scope of the dehydrative allylation reaction using allyl alcohol as allyl donor with [RuCp(PP)]+ complexes as catalysts is explored. Aliphatic alcohols are successfully allylated with allyl alcohol or diallyl ether, obtaining high selectivity for the alkyl allyl ether. The reactivity of aliphatic alcohols is in the order of primary > secondary tertiary. The tertiary alcohol 1-adamantanol reacts extremely slowly in the absence of strong acid, but when HOTs is added, reasonable yields of 1-adamantyl allyl ether are obtained. The alkyl allyl ether is found to be the thermodynamically favored product over diallyl ether. Apart from alcohols, thiols and indole are also efficiently allylated, while aniline acts as a catalyst inhibitor. Allylation reactions with various substituted allylic alcohols give products with retention of the substitution pattern. It is proposed that a Ru(IV) σ-allyl species plays a key role in the mechanism of these allylation reactions.
Van Rijn, Jimmy A.,Guijt, Marieke C.,De Vries, Dwight,Bouwman, Elisabeth,Drent, Eite
experimental part
p. 212 - 219
(2012/04/17)

Cyanuric chloride as promoter for the oxidation of sulfides and deoxygenation of sulfoxides
This Letter discusses the use of cyanuric chloride as an efficient promoter for the chemoselective oxidation of sulfides to the corresponding sulfones in the presence of H2O2 as the terminal oxidant. Sulfoxides were also found to undergo deoxygenation to sulfides with cyanuric chloride and potassium iodide system. The reaction is broad in scope and easy to perform.
Bahrami, Kiumars,Khodaei, Mohammad M.,Sohrabnezhad, Samira
experimental part
p. 6420 - 6423
(2011/12/21)

Vanadium-catalyzed enantioselective oxidation of allyl sulfides
The enantioselective oxidation of allyl sulfides with a vanadyl complex of 3,5-diiodosalicylidene tert-leucinol as a catalyst and aqueous hydrogen peroxide as an oxidant afforded chiral allyl sulfoxides with high enantioselectivities of up to 97.3% ee and moderate yields.
Zeng, Qingle,Gao, Yuxing,Dong, Junyu,Weng, Wen,Zhao, Yufen
experimental part
p. 717 - 721
(2011/08/06)

Highly selective iron-catalyzed synthesis of alkenes by the reduction of alkynes
Herein, the iron-catalyzed reduction of a variety of alkynes with silanes as a reductant has been examined. With a straightforward catalyst system composed of diiron nonacarbonyl and tributyl phosphane, excellent yields and chemoselectivities (>99 %) were obtained for the formation of the corresponding alkenes. After studying the reaction conditions, and the scope and limitations of the reaction, several attempts were undertaken to shed light on the reaction mechanism. Im Rahmen dieser Arbeit wird die Eisen-katalysierte Reduktion von Alkinen zu den entsprechenden Alkenen mit Hilfe von Silanen vorgestellt. Hierbei konnten exzellente Ausbeuten und Selektivitaeten (>99 %) durch die Modifikation des eingesetzten Eisenkatalysators mit Phosphanen beobachtet werden. Nach genauer Untersuchung verschiedenster Reaktionsparameter wurden die hervorragenden Eigenschaften des Katalysatorsystems in der Reduktion zahlreicher Alkine gezeigt. Zum besseren Verstaendnis der Reaktion wurden verschiedene mechanistische Experimente durchgefuehrt. Iron Made′m: In situ generated iron complexes catalyze the reduction of alkynes with silanes as a hydride source with excellent selectivity (>99 %). Copyright
Enthaler, Stephan,Haberberger, Michael,Irran, Elisabeth
experimental part
p. 1613 - 1623
(2012/06/04)

Silica nanoparticles as a reusable catalyst: A straightforward route for the synthesis of thioethers, thioesters, vinyl thioethers and thio-Michael adducts under neutral reaction conditions
A simple and straightforward route for the synthesis of thioethers, thioesters, vinyl thioethers and thio-Michael adducts has been demonstrated using silica nanoparticles (NPs) as a reusable catalyst via the 1,2-addition of thiols to alkenes, alkynes and alkyl/acyl halides, and the 1,4-addition of thiols to conjugated alkenes at room temperature.
Banerjee, Subhash,Das, Jayanta,Alvarez, Richard P.,Santra, Swadeshmukul
experimental part
p. 302 - 306
(2010/06/13)

Silylene transfer to allylic sulfides: Formation of substituted silacyclobutanes
Silylene transfer to allylic sulfides results in a formal 1,2-sulfide migration. The rearrangement yields substituted silacyclobutanes, not the expected silacyclopropanes. The silacyclobutanes were elaborated by insertions of carbonyl compounds selectively into one carbon-silicon bond. A mechanism for the 1,2-sulfide migration is proposed involving an episulfonium ion intermediate.
Ager, Bryan J.,Bourque, Laura E.,Buchner, Kay M.,Woerpel
supporting information; experimental part
p. 5729 - 5732
(2010/11/04)

Silica-promoted facile synthesis of thioesters and thioethers: A highly efficient, reusable and environmentally safe solid support
An efficient, mild and rapid procedure for the acylation and alkylation of aromatic and aliphatic thiols mediated on a silica gel surface at room temperature is described. The protocol allows the protection of thiols under neutral heterogeneous conditions without requiring any bases or Lewis acids, and the silica gel used as the promoter can be recycled for several runs without any loss of activity.
Basu, Basudeb,Paul, Susmita,Nanda, Ashis K.
experimental part
p. 767 - 771
(2010/09/05)

Regio- and enantioselective intermolecular hydroacylation: Substrate-directed addition of salicylaldehydes to homoallylic sulfides
We report a Rh-catalyzed, regio- and enantioselective intermolecular olefin hydroacylation under mild conditions. Hydroacylations between homoallylic sulfides, containing a substrate-bound directing group, and salicylaldehyde derivatives occur in the presence of a spiro-phosphoramidite ligand, (R)-SIPHOS-PE, to give α-branched ketones in >20:1 selectivity and up to 97% ee. Our conditions are also applicable to the asymmetric intermolecular hydroacylation of 1,2-disubstituted olefins.
Coulter, Matthew M.,Kou, Kevin G. M.,Galligan, Baye,Dong, Vy M.
supporting information; experimental part
p. 16330 - 16333
(2011/02/23)

Reactions of 2-(α-Haloalkyl)thiiranes with nucleophilic reagents: V.* Reactions of 2-(α-chloroalkyl)thiiranes with organolithium compounds
2-(α-Haloalkyl)thiiranes reacted with methyl-, butyl-, and phenyllithium to give the corresponding allyl sulfides. The reactions of diastereoisomeric erythro-and threo-2-(1-chloroethyl)thiiranes with phenyllithium were stereospecific, and they afforded (E)-and (Z)-1-phenylsulfanylbut-2-enes, respectively. 3-Chloromethyl-2,2- dimethylthiirane and phenyllithium gave rise to a mixture of 3-methyl-3-phenylsulfanylbut-1-ene and 3-methyl-1-phenylsulfanylbut-2-ene. The reactions of 2-chloromethylthiiranes with phenyllithium and methyllithium in the presence of a catalytic amount of copper(I) iodide (10 mol %) led to the formation of substituted thiiranes as the major products. Mechanisms of the observed transformations are discussed. Pleiades Publishing, Ltd., 2010.
Tomashevskii,Sokolov,Potekhin
experimental part
p. 1822 - 1825
(2011/04/17)

Highly efficient catalytic dehydrative S-allylation of thiols and thioic S-acids
A SH-selective allylation method using [CpRu(2-quinolinecarboxylato) (η3-C3H5)]PF6 has been realized in various solvents including aqueous media to give allyl sulfides and allyl S-thioates, demonstrating the potential applicability to lipopeptide chemistry.
Tanaka, Shinji,Pradhan, Prasun Kanti,Maegawa, Yusuke,Kitamura, Masato
supporting information; experimental part
p. 3996 - 3998
(2010/07/06)

Remarkable activity of the isomerization catalyst [RuCp(PPh 3)2](OTs) in O-allylation of phenol with allyl alcohol
It was surprisingly found that the highly active allyl alcohol redox isomerization catalyst [RuCp(PPh3)2](OTs) upon addition of a catalytic amount of a strong acid can change its catalytic action fully to the selective O-allylation of phenols with allyl alcohol. High turnover numbers (75,000 based on phenol; 200,000 based on allyl alcohol) are reached, and the catalyst is very stable in the presence of substrate. Addition of triphenylphosphine to the reaction mixture does not lead to further stabilization of the catalyst; instead, the free phosphine is rapidly allylated, thereby consuming the acid, which deactivates the catalytic system for allylation reactions. This catalyst with monodentate phosphine ligands is superior in both activity and selectivity to similar catalysts with bidentate phosphine ligands. Apart from phenols, also thiophenol can be efficiently allylated to form allyl phenyl sulfide.
Van Rijn, Jimmy A.,Van Stapele, Esther,Bouwman, Elisabeth,Drent, Eite
experimental part
p. 220 - 226
(2010/09/04)