- THE DIMESITYLBORON GROUP IN ORGANIC SYNTHESIS, IX. A MOST UNUSUAL REACTION : ELECTROPHILIC ATTACK ON SULPHUR IN α-THIOCARBANIONS.
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Predominant alkylation of a boron-stabilised carbanion containing an α-phenylthio group is unprecedentedly on sulphur rather than carbon.Even in lithium phenylthiomethane a similar effect can be observed, its importance being solvent dependant.
- Pelter, Andrew,Bugden, Gina,Pardasani, Ram,Wilson, John
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Read Online
- Visible-light-activated selective synthesis of sulfoxides via thiol-ene/oxidation reaction cascade
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A convenient, highly selective and metal-free synthesis of sulfoxides from alkenes and thiols using NHPI as an inexpensive and reusable organophotoredox catalyst is reported. The protocol involves radical thiol-ene/oxidation reaction cascade and utilizes visible light and air (O2) as inexpensive, readily available, non-toxic and eco-sustainable reagents to afford up to 96% yields of the product at room temperature.
- Singh, Manjula,Yadav, Arvind K.,Yadav, Lal Dhar S.,Singh
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Read Online
- Photoinitiated Thiol-Ene “Click” Reaction: An Organocatalytic Alternative
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The thiol-ene coupling (TEC) reaction has attracted a lot of scientific attention during the last years, particularly in the fields of polymers, materials and more recently in drug design. The combination of organocatalysis and photocatalysis has enabled the development of an efficient synergistic protocol for the addition of various thiols to a plethora of olefins. Utilizing phenylglyoxylic acid as the catalyst-initiator and common household bulbs as the light source, we report an organocatalytic photoinitiated TEC reaction showing exceptional tolerance in the presence of various functionalities, untangling previously unsolved problems. (Figure presented.).
- Limnios, Dimitris,Kokotos, Christoforos G.
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Read Online
- Synthesis of new copper(I) based linear 1-D-coordination polymers with neutral imidazolinium-dithiocarboxylate ligands
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An imidazolinium-dithiocarboxylate betaine has been applied for the first time as a ligand in a coordination polymer with copper(i) halides. The resulting 1-D-coordination compounds show a linear double chain structure with trigonally coordinated copper(i
- Neuba,Ortmeyer,Konieczna,Weigel,Fl?rke,Henkel,Wilhelm
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Read Online
- Nucleophilic substitution by Grignard reagents on sulfur mustards
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With proper activation of the leaving group, sulfur mustards react with Grignard reagents with neighboring group participation of the sulfur atom. 2,6-Dichloro-9-thiabicyclo[3.3.1]nonane is especially useful in this regard, providing clean reactivity with organomagnesium nucleophiles on a topologically constrained scaffold.
- Converse, Antonella,Saaidi, Pierre-Loic,Sharpless, K. Barry,Finn
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Read Online
- Solvent-mediated switching between oxidative addition and addition-oxidation: Access to β-hydroxysulfides and β-arylsulfones by the addition of thiols to olefins in the presence of Oxone
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The reaction between aryl olefins and thiols in the presence of Oxone in toluene-water (9:1, v/v) affords β-hydroxy-2-arylethyl aryl sulfides smoothly by the interception of intermediary thiyl radicals with aryl olefins; the former are generated by the ox
- Moorthy, Jarugu Narasimha,Payra, Soumen,Yadav, Navin
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p. 582 - 591
(2022/01/22)
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- Polynuclear heteroleptic ruthenium(II) photoredox catalysts: Evaluation in blue-light-mediated, regioselective thiol-ene reactions
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Polynuclear heteroleptic ruthenium(II) photosensitisers combining either imine or amine-functionalised bipyridyl ligands were synthesised (via Schiff-base condensation/reductive amination reactions), characterised and investigated for their photoreactivity in the hydrothiolation reaction. Furthermore, electrochemical, electronic absorption and emission studies of the complexes were conducted. All the ligand-modified, heteroleptic complexes show red-shifted emission spectra (614–633 nm) relative to the canonical [Ru(bpy)3](PF6)2 complex (609 nm), attributed to the transition from the triplet MLCT excited state (3MLCT) to the ground state. The complexes were evaluated as visible-light photoredox catalysts in the radical hydrothiolation reaction of olefins (thiol-ene coupling) to afford thioethers. Control reactions performed in the absence of the photocatalyst resulted in either significantly lower yields (6%) or no product formation, demonstrating the role of the complexes as photoredox catalysts. The reactions carried out using trinuclear complexes (Ered (Ru2+*/+) = +0.300 V vs Ag/Ag+) resulted in increased yields in comparison with their respective mononuclear congeners and greater than those reported for [Ru(bpy)3](PF6)2, demonstrating the benefits of using polynuclear photocatalysts for photoinitiated redox catalysis reactions.
- Motimani, Nozuko M.,Ngubane, Siyabonga,Smith, Gregory S.
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supporting information
(2021/12/17)
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- One-Pot Synthesis of N-Iodo Sulfoximines from Sulfides
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This is the first report on the synthesis and characterization of N-iodo sulfoximines. The synthesis was designed as a room temperature one-pot cascade reaction from readily available sulfides as starting compounds, converted into sulfoximines by reaction with ammonium carbonate and (diacetoxyiodo)benzene, followed by iodination with N-iodosuccinimide or iodine in situ, in up to 90% isolated yields, also at a multigram scale. Iodination of aryls with N-iodo sulfoximines, oxidation, and conversion to N-SCF3 congeners have been demonstrated.
- Zupanc, An?e,Jereb, Marjan
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p. 5991 - 6000
(2021/05/05)
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- Facile Thiol–Ene Click Protocol Using Benzil as Sensitizer and White LED as Light Source
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The thiol–ene reaction leading to a series of thioether derivatives by simple metal and oxidant free visible light promoted photosensitized protocol, following anti-Markonikov hydrothiolation of unactivated aryl and alkyl olefins at room temperature is demonstrated. Benzil served as a green photosensitizer in this reaction and white LED lights as a light source. This radical based thiol–ene reaction is operationally simple and tolerates a wide variety of functional groups present in olefins.
- Das, Anupam,Thomas, K. R. Justin
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supporting information
p. 7214 - 7218
(2020/11/30)
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- Chemoselective Homologation-Deoxygenation Strategy Enabling the Direct Conversion of Carbonyls into (n+1)-Halomethyl-Alkanes
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The sequential installation of a carbenoid and a hydride into a carbonyl, furnishing halomethyl alkyl derivatives, is reported. Despite the employment of carbenoids as nucleophiles in reactions with carbon-centered electrophiles, sp3-type alkyl halides remain elusive materials for selective one-carbon homologations. Our tactic levers on using carbonyls as starting materials and enables uniformly high yields and chemocontrol. The tactic is flexible and is not limited to carbenoids. Also, diverse carbanion-like species can act as nucleophiles, thus making it of general applicability.
- Citarella, Andrea,Holzer, Wolfgang,Ielo, Laura,Langer, Thierry,Miele, Margherita,Pace, Vittorio,Urban, Ernst,Zehl, Martin
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supporting information
p. 7629 - 7634
(2020/10/12)
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- Air-stable binuclear Titanium(IV) salophen perfluorobutanesulfonate with zinc power catalytic system and its application to C–S and C–Se bond formation
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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
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- Hydroarylation of alkynes and alkenes through alumina-sulfuric acid catalyzed regioselective C–C bond formation
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A highly atom-efficient synthetic protocol for hydroarylation of terminal-aryl alkynes and styrene through the regioselective C–C bond formation via the electrophilic addition of naphthols and substituted phenols has been developed using alumina-sulfuric acid as a heterogeneous supported solid acid catalyst. This methodology shows excellent regioselectivity and affords the desired product in good to excellent yield. The heterogeneous catalyst can also be recycled efficiently without much loss of activity.
- Pramanik, Amit,Ghatak, Avishek,Khan, Sagar,Bhar, Sanjay
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supporting information
p. 1091 - 1095
(2019/03/26)
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- CATALYTIC C-X-BOND METATHESIS THROUGH ARYLATION
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The present invention refers to a process for a catalytic aryl transfer to rearrange the backbone of aromatic C-X bonds.
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Page/Page column 21; 27
(2018/09/28)
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- Aerial dioxygen activation: Vs. thiol-ene click reaction within a system
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Markovnikov or anti-Markovnikov selective thiol-ene click (TEC) reactions and the synthesis of β-hydroxysulfides via aerial dioxygen activation are prevalent C-S bond forming reactions of styrenes and thiophenols. Herein, by choosing appropriate environme
- Choudhuri, Khokan,Mandal, Arkalekha,Mal, Prasenjit
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supporting information
p. 3759 - 3762
(2018/04/16)
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- Alkyl Sulfides as Promising Sulfur Sources: Metal-Free Synthesis of Aryl Alkyl Sulfides and Dialkyl Sulfides by Transalkylation of Simple Sulfides with Alkyl Halides
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A site-selective metal-free dealkylative approach to synthesize aryl alkyl and symmetrical dialkyl sulfides has been developed. This procedure is convenient and has wide functional group tolerance giving rise to sulfides carrying various alkyl chains from simple alkyl sulfides and alkyl halides in good to excellent yields. This transalkylation proceeds by an ionic mechanism via sulfonium intermediates and it was proposed that dimethylacetamide (DMAC) may participate in part to promote the reaction.
- Liu, Ting,Qiu, Renhua,Zhu, Longzhi,Yin, Shuang-Feng,Au, Chak-Tong,Kambe, Nobuaki
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supporting information
p. 3833 - 3837
(2018/12/05)
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- A Novel Method for the Direct Synthesis of Symmetrical and Unsymmetrical Sulfides and Disulfides from Aryl Halides and Ethyl Potassium Xanthogenate
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An efficient and new method for the synthesis of disulfides and sulfides via the reaction of aryl halides with ethyl potassium xanthogenate in the presence of MOF-199 is described. O -Ethyl- S -aryl carbonodithioate has a key role as an intermediate in this procedure; it was converted into symmetrical diaryl disulfides in DMF. Additionally, this could be applied to the synthesis of unsymmetrical aryl alkyl(aryl′) disulfides by the reaction with S -alkyl(aryl) sulfurothioates (Bunte salts) as well as unsymmetrical aryl alkyl(aryl′) sulfides in DMSO.
- Soleiman-Beigi,Arzehgar
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supporting information
p. 986 - 992
(2018/02/09)
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- Modified conditions for copper-catalyzed ipso-thiolation of arylboronic acid esters with thiosulfonates
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An efficient ipso-thiolation of arylboronic acid esters with thiosulfonates has been achieved under mild and odorless conditions using a copper catalyst. The use of TMEDA and cesium fluoride as the ligand and base, respectively, dramatically facilitated the desired transformation. The method exhibited a broad substrate scope, which allowed for the expeditious synthesis of diverse aryl sulfides from easily available starting materials.
- Kanemoto, Kazuya,Yoshida, Suguru,Hosoya, Takamitsu
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supporting information
p. 85 - 88
(2018/01/26)
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- Visible light photocatalysis with benzophenone for radical thiol-ene reactions
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We report herein a simple, metal- and oxidant-free visible light promoted strategy for an anti-Markovnikov hydrothiolation of unactivated olefins using benzophenone as an inexpensive photocatalyst at room temperature. Anti-Markovnikov adducts of a wide va
- Singh, Manjula,Yadav, Arvind K.,Yadav, Lal Dhar S.,Singh
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supporting information
p. 2206 - 2208
(2017/05/16)
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- Sulfamic acid: An efficient and recyclable catalyst for the regioselective hydrothiolation of terminal alkenes and alkynes with thiols
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Herein, we described a new method for the preparation of thioethers through hydrothiolation of alkenes and alkynes, using sulfamic acid as a reusable catalyst. Generally, this new methodology afforded the desired products in very good yields, under metal
- Rosa, Clarissa Helena,Peixoto, Maura Luise B.,Rosa, Gilber Ricardo,Godoi, Benhur,Galetto, Fábio Zazyki,D'Oca, Marcelo Gon?alves Montes,Godoi, Marcelo
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supporting information
p. 3777 - 3781
(2017/09/09)
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- Metal–organic framework MOF-199-catalyzed direct and one-pot synthesis of thiols, sulfides and disulfides from aryl halides in wet polyethylene glycols (PEG 400)
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A highly porous metal–organic frame work Cu3 BTC2 (copper(II)-benzene-1,3,5-tricarboxylate) that is known as MOF-199 was synthesized from the reaction of 1,3,5-benzenetricarboxylic acid and Cu(OAc)2·H2O by a solvothermal method and characterized by several techniques including FT-IR, XRD, EDX and scanning electron microscopy. The MOF-199 used as an efficient catalyst for one-pot synthesis of thiols by domino reactions of aryl halides and thiourea, and subsequently conversion to aryl alkyl sulfides and diaryl disulfides in polyethylene glycols (PEGs). A variety of aryl alkyl sulfides can be obtained in good to excellent yields in a relatively short reaction time and in the presence of the trace amount of catalyst. Also, the catalyst can be separated from the reaction mixture by decanting, and be reused without significant degradation in catalytic activity.
- Soleiman-Beigi, Mohammad,Sadeghizadeh, Fatemeh,Basereh, Ali
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p. 572 - 583
(2017/09/27)
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- Acid-Catalyzed Oxidative Addition of Thiols to Olefins and Alkynes for a One-Pot Entry to Sulfoxides
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An oxidative variant of the thiol-ene reaction has been developed, achieving the direct addition of thiols to olefins to form sulfoxides. The reaction uses tert-butyl hydroperoxide as oxidant and methanesulfonic acid as catalyst. The latter is believed to catalyze the oxidation of the intermediate sulfide to the sulfoxide. No special precautions are necessary to exclude oxygen, yet the products are formed without oxidation at the β-position. Styrenes, acrylic acid derivatives, alkynes, and thiophenols gave the highest yields, while aliphatic olefins and thiols were less effective.
- Yue, Hui-Lan,Klussmann, Martin
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supporting information
p. 2505 - 2509
(2016/10/24)
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- Hydrothiolation of Alkenes and Alkynes Catalyzed by 3,4-Dimethyl-5-vinylthiazolium iodide and Poly(3,4-dimethyl-5-vinylthiazolium) iodide
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The highly selective anti-Markovnikov addition of thiols to unactivated alkenes and alkynes was demonstrated by using 3,4-dimethyl-5-vinylthiazolium iodide or its polymer, poly(3,4-dimethyl-5-vinylthiazolium) iodide, as a complementary catalyst. The reaction proceeded cleanly under base-free conditions in air with both aromatic and aliphatic thiols. The polymer catalyst showed a high turnover number (≈5800) and could be reused up to four times without any loss of catalytic activity. DFT calculations supported stabilization of the thiyl radical intermediate by the thiazolium cation, which resulted in reaction of the radical with unsaturated C?C bonds.
- Chun, Supill,Chung, Junyong,Park, Ji Eun,Chung, Young Keun
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p. 2476 - 2481
(2016/08/24)
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- Regioselective Thiocarbonylation of Vinyl Arenes
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A palladium-catalyzed thiocarbonylation of styrene derivatives is reported for the first time. The combination of thiols as nucleophiles and a bidentate ligand ensures a unique reaction outcome with high regioselectivity toward the more valuable branched isomer and new reactivity. The ambient reaction conditions (temperature, catalyst loading) and the use of a CO surrogate render this transformation a useful method for the synthesis of thioesters from available feedstock. Various functional groups on arene and thiol substituents are tolerated by the system. Notably, challenging ortho-substituted styrenes are converted with unprecedentedly high regioselectivity.
- Hirschbeck, Vera,Gehrtz, Paul H.,Fleischer, Ivana
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supporting information
p. 16794 - 16799
(2017/01/10)
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- Catalyst-Free Difunctionalization of Activated Alkenes in Water: Efficient Synthesis of β-Keto Sulfides and Sulfones
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Difunctionalization of activated alkenes, a powerful strategy in chemical synthesis, has been accomplished for direct synthesis of a series of β-keto sulfides and β-keto sulfones. The transformation, mediated by O2, proceeds smoothly in water and without any catalyst. Prominent advantages of this method include mild reaction conditions, purification simplicity, and gram-scale synthesis, underlining the practical utility of this methodology.
- Wang, Huamin,Wang, Guangyu,Lu, Qingquan,Chiang, Chien-Wei,Peng, Pan,Zhou, Jiufu,Lei, Aiwen
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p. 14489 - 14493
(2016/10/03)
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- Thiol-ene "click" reaction triggered by neutral ionic liquid: The "ambiphilic" character of [hmim]br in the regioselective nucleophilic hydrothiolation
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Thiol-ene "click" chemistry has emerged as a powerful strategy to construct carbon-heteroatom (C-S) bonds, which generally results in the formation of two regioisomers. To this end, the neutral ionic liquid [hmim]Br has been explored as a solvent cum catalyst for the synthesis of linear thioethers from activated and inactivated styrene derivatives or secondary benzyl alcohols and thiols without the requirement of using a metal complex, base, or free radical initiator. Furthermore, detailed mechanistic investigations using 1H NMR spectroscopy and quadrupole time-of-flight electrospray ionization mass spectrometry (Q-TOF ESI-MS) revealed that the "ambiphilic" character of the ionic liquid promotes the nucleophilic addition of thiol to styrene through an anti-Markovnikov pathway. The catalyst recyclability and the extension of the methodology for thiol-yne click chemistry are additional benefits. A competitive study among thiophenol, styrene, and phenyl acetylene revealed that the rate of reaction is in the order of thiol-yne a?a thiol-ene a?a dimerization of thiol in [hmim]Br.
- Kumar, Rajesh,Saima,Shard, Amit,Andhare, Nitin H.,Richa,Sinha, Arun K.
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supporting information
p. 828 - 832
(2015/02/05)
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- Transition metal photoredox catalysis of radical thiol-ene reactions
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We describe the anti-Markovnikov hydrothiolation of olefins using visible-light-absorbing transition metal photocatalysts. The key thiyl radical intermediates are generated upon quenching of photoexcited Ru*(bpz) 32 with a variety of thiols. The adducts of a wide variety of olefins and thiols are formed in excellent yield (73-99%).
- Tyson, Elizabeth L.,Ament, Michael S.,Yoon, Tehshik P.
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p. 2046 - 2050
(2013/03/29)
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- Amberlyst-15: An efficient heterogeneous reusable catalyst for selective anti-Markovnikov addition of thiols to alkenes/alkynes and for thiolysis of epoxides
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The anti-Markovnikov addition of thiols to alkenes/alkynes and thiolysis of epoxides is described using Amberlyst-15 as a selective, commercially available, inexpensive and reusable catalyst. The products like diorganyl sulphides, β-hydroxy sulphides and phenyl(styryl)sulfanes were obtained in good to excellent yields in short reaction time and with high regio-selectivity. The catalyst was reused up to five consecutive recycles without any loss in its catalytic activity. The developed methodology is a metal free protocol for C-S bond formation reaction with high atom economy.
- Lanke, Satish R.,Bhanage, Bhalchandra M.
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- 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
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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.
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supporting information; experimental part
p. 2149 - 2152
(2012/05/05)
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- 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
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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
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experimental part
p. 302 - 306
(2010/06/13)
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- Solvent-free anti-markovnikov addition of thiols to alkenes using anhydrous cerium(III) chloride as catalyst
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The anti-Markovnikov addition of thiols to alkenes using CeCl3 as catalyst is described. The products were obtained in good to excellent yields. The reaction occurred under solvent-free conditions at room temperature.
- Silveira, Claudio C.,Mendes, Samuel R.,Líbero, Francieli M.
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experimental part
p. 790 - 792
(2010/06/13)
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- Exploring chromium(III)-alkyl bond homolysis with CpCr[(ArNCMe) 2CH](R) complexes
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A range of paramagnetic Cr(III) monohydrocarbyl complexes CpCr[(ArNCMe)2CH](R) (Ar = ortho-disubstituted aryl; R = primary alkyl, trimethylsilylmethyl, benzyl, phenyl, alkenyl, or alkynyl) were synthesized to investigate how varying the steric and electronic properties of the R group affected their propensity for Cr-R bond homolysis. Most complexes were prepared by salt metathesis of known CpCr[(ArNCMe)2CH](Cl) compounds in Et2O with commercial RMgCl solutions, although more sterically demanding combinations of Ar and R groups necessitated the use of halide-free MgR2 reagents and the Cr(III) tosylate or triflate derivatives. Alternative synthetic routes to Cr(III)-R species using the previously reported Cr(II) compounds CpCr[(ArNCMe)2CH] and sources of R? radicals (e.g., BEt3 and air) were also explored. The UV-vis spectra of the CpCr[(ArNCMe)2CH](R) complexes possessed two strong bands with maximum absorbances in the ranges 395-436 nm and 535-582 nm, with the band in the latter range being particularly characteristic of the Cr(III)-R compounds. The Cr-CH2R bond lengths as determined by single-crystal X-ray diffraction were longer than those in the corresponding Cr-CH3 complexes, typically falling in the range 2.10 to 2.13 A. The Cr(III) benzyl compounds displayed longer Cr-CH2Ph distances, while the bond lengths for the alkenyl and alkynyl species were substantially shorter. The rate of Cr-R bond homolysis at room temperature was determined by monitoring the reaction of Cr(III) neopentyl, benzyl, and isobutyl complexes with excess PhSSPh using UV-vis spectroscopy. Although the other primary alkyl, phenyl, and alkenyl compounds did not undergo appreciable homolysis under these conditions, they were cleanly converted to CpCr[(ArNCMe)2CH](SPh) by photolysis.
- MacLeod, K. Cory,Conway, Julia L.,Patrick, Brian O.,Smith, Kevin M.
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scheme or table
p. 17325 - 17334
(2011/03/01)
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- Native silica nanoparticle catalyzed anti-Markovnikov addition of thiols to inactivated alkenes and alkynes: a new route to linear and vinyl thioethers
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A new route for the synthesis of linear and vinyl thioethers has been demonstrated using bare silica nanoparticle as catalyst at room temperature under solvent-free conditions. The catalyst can be reused up to six times without loss of catalytic activity.
- Banerjee, Subhash,Das, Jayanta,Santra, Swadeshmukul
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body text
p. 124 - 127
(2009/04/14)
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- One-pot synthesis of β-hydroxysulfides from styrenes and disulfides using the Zn/AlCl3 system
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A simple, general, and highly regioselective procedure has been developed for the one-pot synthesis of β-hydroxysulfides in good yields from various styrenes and disulfides by cleavage of the S-S bond with a Zn/AlCl3 system in aqueous acetonitr
- Movassagh, Barahman,Navidi, Mozhgan
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scheme or table
p. 6712 - 6714
(2009/04/07)
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- Convenient synthesis of unsymmetrical organochalcogenides using organoboronic acids with dichalcogenides via cleavage of the S-S, Se-Se, or Te-Te bond by a copper catalyst
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(Chemical Equation Presented) This article describes the methodology for a copper-catalyzed preparation of numerous monochalcogenides from dichalcogenides with organoboronic acids. Unsymmetrical diorgano-monosulfides, selenides, and tellurides can be synthesized by the coupling of dichalcogenides with aryl- or alkylboronic acids using a copper catalyst in air. The present reaction can take advantage of both organochalcogenide groups on dichalcogenide.
- Taniguchi, Nobukazu
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p. 1241 - 1245
(2007/10/03)
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- Water-promoted highly selective anti-Markovnikov addition of thiols to unactivated alkenes
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The highly selective anti-Markovnikov addition of thiols to unactivated alkenes is demonstrated in water at room temperature without any additive. This is a very simple and efficient method for the synthesis of linear thioethers. Georg Thieme Verlag Stuttgart.
- Ranu, Brindaban C.,Mandal, Tanmay
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p. 925 - 928
(2008/02/02)
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- Aryl- or alkylation of diaryl disulfides using organoboronic acids and a copper catalyst
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A variety of unsymmetrical monosulfides can be synthesized in good yields by copper-catalyzed coupling of disulfides with organoboronic acids in air. Furthermore, this method can result in the successful aryl- or alkylation of both organosulfide groups in a disulfide. Georg Thieme Verlag Stuttgart.
- Taniguchi, Nobukazu
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p. 1351 - 1354
(2007/10/03)
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- Indium(I) iodide promoted cleavage of dialkyl/diaryl disulfides and subsequent anti-Markovnikov addition to styrenes: a new route to linear thioethers
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The reaction of thiolate anions, generated in situ by indium(I) iodide promoted cleavage of dialkyl/diaryl disulfides, with styrenes has been investigated. Thiolate anions add to a variety of styrenes in an anti-Markovnikov manner producing linear thioethers in high yields. This method provides a new route to the synthesis of thioethers.
- Ranu, Brindaban C.,Mandal, Tanmay
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p. 6911 - 6914
(2007/10/03)
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- Ionic liquid as catalyst and reaction medium: A simple, convenient and green procedure for the synthesis of thioethers, thioesters and dithianes using an inexpensive ionic liquid, [pmIm]Br
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An easily accessible and inexpensive room temperature ionic liquid, 1-pentyl-3-methylimidazolium bromide, [pmIm]Br efficiently catalyzes the reaction of alkyl halides or acyl halides with thiols without any solvent at room temperature leading to the synthesis of thioethers and thioesters in high yields. This reaction has also been extended for the preparation of dithianes and transthioetherification. The ionic liquid is recovered and recycled for subsequent runs.
- Ranu, Brindaban C.,Jana, Ranjan
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p. 1811 - 1818
(2007/10/03)
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- Trimethylchlorosilane (TMCS) catalyzed efficient reduction of sulfoxides to thioethers using 3-mercaptopropionic acid under mild reaction conditions
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A variety of alkyl and aryl sulfoxides were successfully deoxygenated using 3-mercaptopropionic acid as reducing agent and a catalytic amount of trimethylchlorosilane (10-20 mol%) in CH3CN at ambient temperature.
- Karimi, Babak,Zareyee, Daryoush
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- N-bromosuccinimide and iodine catalyzed highly efficient deoxygenation of sulfoxides to thioethers using 3-mercaptopropionic acid under mild reaction conditions
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A variety of alkyl and aryl sulfoxides have been successfdlly deoxygenated using 3-mercaptopropionic acid as a reducing agent and a catalytic amount of either NBS or I2 (5-10 mol%) in MeCN at ambient temperature. Under the described reaction condition, acid sensitive substrates such as acetals remained intact after several hours.
- Karimi, Babak,Zareyee, Daryoush
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p. 1875 - 1877
(2007/10/03)
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- Rapid, efficient and chemoselective deoxygenation of sulfoxides to thioethers using NaBH4/I2
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Sodium borohydride in the presence of iodine in anhydrous THF converts a range of structurally different sulfoxides to their thioethers in excellent yields. It has been found that chemoselective deoxygenation of sulfoxides can be achieved in the presence of other reducible functional groups such as esters, nitriles and double bonds.
- Karimi, Babak,Zareyee, Daryoush
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p. 335 - 336
(2007/10/03)
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- Intramolecular assistance of electron transfer from heteroatom compounds. Electrochemical oxidation of 2-(2-pyridyl)ethyl-substituted ethers, sulfides, and selenides
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Organoheteroatom compounds having a 2-(2-pyridyl)ethyl group were synthesized and their oxidation potentials were determined by rotating disk electrode voltammetry. The oxidation potentials were found to be less positive than those of the corresponding compounds having a phenyl group in place of the pyridyl group. The dynamic coordination of the pyridyl group to the heteroatom, which stabilizes the cation radical intermediate, seems to be responsible for facilitating the electron transfer. The magnitude of the intramolecular assistance increases along with an increase in the oxidation potential of the parent compounds. This tendency can be explained in terms of the energy match between the nonbonding p orbital of the pyridyl nitrogen and the HOMO of the parent heteroatom compound.
- Watanabe, Mitsuru,Suga, Seiji,Yoshida, Jun-Ichi
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p. 243 - 247
(2007/10/03)
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- Anti-Markovnikov addition of thiols across double bonds catalyzed by H- Rho-zeolite
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A variety of olefins react with thiols in the presence of a catalytic amount of H-Rho-zeolite to afford the corresponding anti-Markovnikov addition products in good to excellent yields.
- Kumar, Pradeep,Pandey, Rajesh Kumar,Hegde, Vishnumurthy R.
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p. 1921 - 1922
(2007/10/03)
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- Efficient deoxygenation of sulfoxides to thioethers and reductive coupling of sulfonyl chlorides to disulfides with tungsten hexachloride
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Tungsten hexachloride (WCI6) in the presence of NaI in anhydrous acetonitrile or zinc powder in anhydrous THF converts sulfoxides to their thioethers in high yields. Reductive coupling of sulfonyl chlorides to their corresponding disulfides is also achieved efficiently with the above reagent in anhydrous acetonitrile in high yields. Sodium benzene sulfinate as a model compound for sulfinate salts is also converted to diphenyl disulfide in almost quantitative yield.
- Firouzabadi, Habib,Karimi, Babak
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p. 500 - 502
(2007/10/03)
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- Nucleophilic substitution of protected β-bromoethyl cyclohexadiene-cis-diol as an alternative to direct microbial oxidation of β-functionalized phenethyl substrates
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(5S,6R)-1-(2-Bromoethyl)-5,6-(propane-2,2-diyldioxy)cyclohexa-1,3-diene 6 is subjected to nucleophilic substitution reaction using C-, N-, O- and S-based nucleophiles. The yields of the products are compared with those obtained by direct microbial oxidation of the corresponding aromatic substrates. The enantiomeric excess and isolated yield for each compound are reported.
- Hudlicky, Tomas,Endoma, Mary Ann A.,Butora, Gabor
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p. 2187 - 2192
(2007/10/03)
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- SYNTHESIS OF SULFOXIDES BY PHASE TRANSFER CATALYZED OXIDATION OF SULFIDES BY CERIUM (IV) AMMONIUM NITRATE
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Diaryl, dialkyl and alkyl aryl sulfides are oxidized by cerium(IV) ammonium nitrate in H2O/CH2Cl2, in the presence of tetra-n-butylammonium bromide, at room temperature, to give sulfoxides in yields ranging between 90 and 100percent.
- Baciocchi, Enrico,Piermattei, Alessandro,Ruzziconi, Renzo
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p. 2167 - 2172
(2007/10/02)
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- Process for preparing thio, dithio or carbonyl compounds
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A process is disclosed for the preparation of compounds of the Formula I wherein X is thio, dithio or carbonyl and R and R1 are defined hereinbelow which comprises reducing a compound of the Formula II wherein A is chlorosulfonyl or a group of the Formula STR1 with a sulfur compound comprising sulfur which is of the (+)4 oxidation degree and is converted into the (+)6 oxidation degree during the process or with a sulfur compound which is decomposed in acidic medium to a compound of the latter oxidation degree in the presence of a catalytic amount but not more than 0.5 mole--related to 1 mole of the starting material of the Formula II--of elemental iodine or a compound capable of delivering hydrogen iodide in acidic medium or a compound which can be reduced to hydrogen iodide in acidic medium with the sulfur compound used.
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- DIRECT CONVERSION OF CARBOXYLIC ACIDS AND CARBOXYLIC ESTERS INTO S,S'-DIPHENYL ACETALS AND PHENYL SULFIDES WITH THEXYLPHENYLTHIOBORANE
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Reaction of carboxylic acids with thexylphenylthioborane in methylene chloride at room temperature gives S,S-diphenyl acetals in high yields and carboxylic esters are converted into phenyl sulfides in the presence of zinc iodide under similar conditions.
- Kim, Sunggak,Kim, Sung Soo
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p. 1913 - 1916
(2007/10/02)
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- ORGANOMETALLICS IN ORGANIC SYNTHESIS. APPLICATIONS OF A NEW DIORGANOZINC REACTION TO THE SYNTHESIS OF C-GLYCOSYL COMPOUNDS WITH EVIDENCE FOR AN OXONIUM-ION MECHANISM
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The mechanistic and stereochemical features of a new organozinc-based substitution process 1,R2)-SPh + R32Zn --> heteroatom-C-(R1,R2,R3)>, first discovered during a total synthesis of the alkaloid mycotoxin α-cyclopiazonic acid, are described.Phenyl thioglycosides were valuable substrates in studying the nature of this reaction process.Since these sulfur compounds are converted into C-glycosyl compounds with some degree of stereoselectivity, the organozinc chemistry does provide a new entry to these biologically active substances.
- Kozikowski, Alan P.,Konoike, Toshiro,Ritter, Allen
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p. 109 - 124
(2007/10/02)
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