- Catalytic conversion of alkynes to α-vinyl sulfides mediated by carbene-linker-carbene (CXC) rhodium and iridium complexes
-
The catalytic activity of a set of mono- and bimetallic Rh(i) and Ir(i) complexes bearing carbene-linker-carbene (CXC) bis-triazolylidene ligands (with X = O, N) coordinated in a bridging or chelating fashion was evaluated in the hydrothiolation of alkyne
- Tolley, Lewis C.,Fernández, Israel,Bezuidenhout, Daniela I.,Guisado-Barrios, Gregorio
-
p. 516 - 523
(2021/02/09)
-
- Continuous Flow Sodiation of Substituted Acrylonitriles, Alkenyl Sulfides and Acrylates
-
The sodiation of substituted acrylonitriles and alkenyl sulfides in a continuous flow set-up using NaDA (sodium diisopropylamide) in EtNMe2 or NaTMP (sodium 2,2,6,6-tetramethylpiperidide)?TMEDA in n-hexane provides sodiated acrylonitriles and alkenyl sulfides, which are subsequently trapped in batch with various electrophiles such as aldehydes, ketones, disulfides and allylic bromides affording functionalized acrylonitriles and alkenyl sulfides. This flow-procedure was successfully extended to other acrylates by using Barbier-type conditions.
- Harenberg, Johannes H.,Weidmann, Niels,Karaghiosoff, Konstantin,Knochel, Paul
-
supporting information
p. 731 - 735
(2020/11/30)
-
- Sulfur?oxygen interaction-controlled (Z)-selectiveanti-Markovnikov vinyl sulfides
-
The sulfur oxygen (S?O) interaction was used herein to obtain (Z)-selectiveanti-Markovnikov vinyl sulfides from the addition of thiyl radicals to terminal alkynes. DFT calculations predicted that S?O interaction originated from the delocalization of the lone-pair of the carbonyl oxygen to the adjacent σ* orbital of the S atom of C-S.
- Pramanik, Milan,Mathuri, Ashis,Mal, Prasenjit
-
supporting information
p. 5698 - 5701
(2021/06/16)
-
- Selectivity control in thiol-yne click reactions: Via visible light induced associative electron upconversion
-
An associative electron upconversion is proposed as a key step determining the selectivity of thiol-yne coupling. The developed synthetic approach provided an efficient tool to access a comprehensive range of products-four types of vinyl sulfides were prepared in high yields and selectivity. We report practically important transition-metal-free regioselective thiol-yne addition and formation of the demanding Markovnikov-type product by a radical photoredox process. The photochemical process was directly monitored by mass-spectrometry in a specially designed ESI-MS device with green laser excitation in the spray chamber. The proposed reaction mechanism is supported by experiments and DFT calculations. This journal is
- Ananikov, Valentine P.,Burykina, Julia V.,Gordeev, Evgeniy G.,K?nig, Burkhard,Shlapakov, Nikita S.
-
p. 10061 - 10070
(2020/10/13)
-
- Facile Thiol–Ene Click Protocol Using Benzil as Sensitizer and White LED as Light Source
-
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
-
supporting information
p. 7214 - 7218
(2020/11/30)
-
- A Simplified Protocol for the Stereospecific Nickel-Catalyzed C-S Vinylation Using NiX 2 Salts and Alkyl Phosphites
-
A Ni-catalyzed C-S cross-coupling using only NiI 2 (0.5-2.5 molpercent) and P(O i Pr) 3 (2.0-10.0 molpercent) is reported. Using an air-stable Ni(II) precatalyst, and a cheap and commercially available ligand, a scalable and robust method was developed to cross-couple various thiophenols and styryl bromides, including some sterically encumbered thiols, an α-bromocinnamaldehyde as well as a thiolation-cyclization.
- Larin, Egor M.,Lautens, Mark,Marchese, Austin D.,Mirabi, Bijan
-
p. 311 - 319
(2019/12/28)
-
- Electrophilic Vinylation of Thiols under Mild and Transition Metal-Free Conditions
-
The iodine(III) reagents vinylbenziodoxolones (VBX) were employed to vinylate a series of aliphatic and aromatic thiols, providing E-alkenyl sulfides with complete chemo- and regioselectivity, as well as excellent stereoselectivity. The methodology displays high functional group tolerance and proceeds under mild and transition metal-free conditions without the need for excess substrate or reagents. Mercaptothiazoles could be vinylated under modified conditions, resulting in opposite stereoselectivity compared to previous reactions with vinyliodonium salts. Novel VBX reagents with substituted benziodoxolone cores were prepared, and improved reactivity was discovered with a dimethyl-substituted core.
- Castoldi, Laura,Di Tommaso, Ester Maria,Gr?fen, Barbara,Olofsson, Berit,Reitti, Marcus
-
supporting information
p. 15512 - 15516
(2020/06/23)
-
- Acetylene and terminal alkyne complexes of copper(i) supported by fluorinated pyrazolates: Syntheses, structures, and transformations
-
Trinuclear {μ-[3,5-(CF3)2Pz]Cu}3 reacts with acetylene to produce the 2:1 copper(i) acetylene complex, Cu4(μ-[3,5-(CF3)2Pz])4(μ-HCCH)2. Related Cu4(μ-[4-Br-3,5-(CF3)2Pz])4(μ-HCCH)2 and Cu4(μ-[4-Cl-3,5-(CF3)2Pz])4(μ-HCCH)2 have also been isolated using the corresponding copper(i) pyrazolate and acetylene. The 1:1 adducts Cu2(μ-[3,5-(CF3)2Pz])2(HCCH)2 and Cu2(μ-[4-Br-3,5-(CF3)2Pz])2(HCCH)2 are significantly less stable to the acetylene loss and can be observed in solution at low temperatures under excess acetylene. The X-ray crystal structures of 2:1 and 1:1 complexes, Cu4(μ-[3,5-(CF3)2Pz])4(μ-HCCH)2 and Cu2(μ-[4-Br-3,5-(CF3)2Pz])2(HCCH)2 are reported. Raman data show a reduction in CC stretching frequency by about ~340 and ~163 cm-1 in the 2:1 and 1:1 Cu(i)/acetylene complexes, respectively, from that of the free acetylene. Copper(i) pyrazolate complexes of the terminal alkynes, phenylacetylene, 1,8-nonadiyne, and 1,7-octadiyne are also reported. They form adducts involving one copper atom on each alkyne moiety. The {μ-[3,5-(CF3)2Pz]Cu}3 is also a very versatile and competent catalyst for alkyne transformations as evident from its ability to catalyze the alkyne C(sp)-H bond carboxylation chemistry with CO2, azide-alkyne cycloadditions leading to 1,2,3-triazoles including the use of acetylene itself as a substrate, and thiol addition to phenylacetylene affording vinyl sulfides.
- Parasar, Devaborniny,Ponduru, Tharun T.,Noonikara-Poyil, Anurag,Jayaratna, Naleen B.,Dias, H.V. Rasika
-
supporting information
p. 15782 - 15794
(2019/11/11)
-
- Gem-Heterosubstituted (stannyl)methylsilanes as synthetic equivalents of functionalized α-stannyl(methyl) anions
-
α-Heterosubstituted silyl derivatives, such as phenylthio-, phenylseleno- and benzotriazolyl-stannyl silanes, react with aldehydes under tetra-n-butylammonium fluoride (TBAF) catalysis, leading to α-substituted-βhydroxy stannanes, able to behave as precursors of Z- and E-olefins, generated by deoxystannylation. This reactivity shows the capability of such heterosubstituted silanes to act as masked carbanions through a mild functionalization of the carbon-silicon bond.
- Tanini, Damiano,Nocentini, Tiziano,Capperucci, Antonella
-
-
- Structural elucidation of supported Rh complexes derived from RhCl(PPh3)3 immobilized on surface-functionalized SBA-15 and their catalytic performance for C-heteroatom (S, O) bond formation
-
The local structures of rhodium complexes derived from the immobilization of Wilkinson's complex, RhCl(PPh3)3, on SBA-15 silica functionalized with primary–amine, secondary–amine, or diphenylphosphine groups within the mesoporous channels were characterized by a series of techniques including XRD, HR-TEM, multinuclear (13C/29Si/31P) solid-state NMR, 2D 31P{1H} HETCOR NMR, XPS, and Rh K-edge EXAFS. Immobilization of RhCl(PPh3)3 through covalent bond formation with different functional groups grafted to the silica surface lead to variations in the local structure of the Rh center that has important implications for catalysis. The immobilized Rh complexes demonstrated high activity for the addition of alkynes with thiols (hydrothiolation) or sulfonic acids (hydrosulfonation) with excellent regio- and stereoselectivity under mild reaction conditions. This work demonstrates the elucidation of the local structure of the immobilized Rh complexes requires a complimentary multi-technique characterization approach that probes both the metal center itself and surrounding ligands.
- Yang, Yong,Chang, Ji Wong,Rioux, Robert M.
-
-
- N-heterocyclic carbene-catalyzed regio- and stereoselective hydrothiolation reaction of alkynes
-
N-heterocyclic carbenes (NHCs) have been utilized as Br?nsted base to catalyze the hydrothiolation reaction between alkynes and thiols to produce the vinyl sulfides stereoselectively.
- Cong, Zi-Song,Zhang, Yang,Du, Guang-Fen,Gu, Cheng-Zhi,He, Lin
-
supporting information
p. 1838 - 1846
(2018/06/25)
-
- General Synthesis of Alkenyl Sulfides by Palladium-Catalyzed Thioetherification of Alkenyl Halides and Tosylates
-
The cross-coupling reaction of alkenyl bromides with thiols catalyzed by palladium complexes derived from inexpensive dppf ligand is reported. These reactions occur under low catalyst loading and in high yields and display wide scope, including the coupling of bulky thiols and trisubstituted bromoolefins, and functional group tolerance. In addition, the thioetherification of less reactive chloroalkenes and, for the first time, alkenyl tosylates was accomplished using a catalyst generated from CyPFtBu alkylbisphosphine ligand.
- Velasco, Noelia,Virumbrales, Cintia,Sanz, Roberto,Suárez-Pantiga, Samuel,Fernández-Rodríguez, Manuel A.
-
supporting information
p. 2848 - 2852
(2018/05/29)
-
- Palladium- and Nickel-Catalyzed Decarbonylative C-S Coupling to Convert Thioesters to Thioethers
-
This Letter describes the development of a catalytic decarbonylative C-S coupling reaction that transforms thioesters into thioethers. Both Pd- and Ni-based catalysts are developed and applied to the construction of diaryl, aryl alkyl, and heterocycle-containing thioethers.
- Ichiishi, Naoko,Malapit, Christian A.,Wo?niak, Aukasz,Sanford, Melanie S.
-
supporting information
p. 44 - 47
(2018/01/17)
-
- Regioselective hydrothiolation of terminal acetylene catalyzed by magnetite (Fe3O4) nanoparticles
-
Herein, we report a new and solvent-free methodology for the preparation of vinyl thioethers from terminal alkynes and thiols, using magnetite (Fe3O4) nanoparticles as a recyclable catalyst. With this greener method, the desired viny
- Rocha, Manuela S. T.,Rafique, Jamal,Saba, Sumbal,Azeredo, Juliano B.,Back, Davi,Godoi, Marcelo,Braga, Antonio L.
-
supporting information
p. 291 - 298
(2017/02/10)
-
- Sulfamic acid: An efficient and recyclable catalyst for the regioselective hydrothiolation of terminal alkenes and alkynes with thiols
-
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
-
supporting information
p. 3777 - 3781
(2017/09/09)
-
- Acid/Phosphide-Induced Radical Route to Alkyl and Alkenyl Sulfides and Phosphonothioates from Sodium Arylsulfinates in Water
-
A newly developed aqueous system with acid and phosphide was introduced in which odorless and stable sodium arylsulfinates can in situ generate arylsulfenyl radicals. These radicals have high reactivity to react with alkynes, alkenes, and H-phosphine oxides for the synthesis of alkyl and alkenyl sulfides and phosphonothioates. The control experiments and quantum calculations are also performed to gain insights into the generation mechanism of arylsulfenyl radicals. Notably, the chemistry is free of thiol odors, organic solvents, and metals.
- Lin, Ya-Mei,Lu, Guo-Ping,Wang, Gui-Xiang,Yi, Wen-Bin
-
p. 382 - 389
(2017/04/26)
-
- A rhodium(i)-oxygen adduct as a selective catalyst for one-pot sequential alkyne dimerization-hydrothiolation tandem reactions
-
An air-stable rhodium(i)-oxygen adduct featuring a CNC-pincer ligand, based on 1,2,3-triazol-5-ylidenes, catalyzes the homo-dimerization and hydrothiolation of alkynes, affording the gem-enyne and α-vinyl sulfide isomers, respectively, with excellent selectivity. A one-pot stepwise strategy allows the selective catalytic preparation of non-symmetric bis-vinyl sulfides, as well as the alkyne dimerization-hydrothiolation tandem reactions.
- Kleinhans, George,Guisado-Barrios, Gregorio,Liles, David C.,Bertrand, Guy,Bezuidenhout, Daniela I.
-
supporting information
p. 3504 - 3507
(2016/03/04)
-
- Mechanistic insight into the pyridine enhanced α-selectivity in alkyne hydrothiolation catalysed by quinolinolate-rhodium(I)-N-heterocyclic carbene complexes
-
RhI-NHC-olefin complexes bearing a N,O-quinolinolate bidentate ligand have been prepared from [Rh(μ-OH)(NHC)(η2-olefin)]2 precursors (olefin = cyclooctene, ethylene). The disposition of the chelate ligand with regard to the carbene i
- Palacios, Laura,Di Giuseppe, Andrea,Artigas, María José,Polo, Victor,Lahoz, Fernando J.,Castarlenas, Ricardo,Pérez-Torrente, Jesús J.,Oro, Luis A.
-
p. 8548 - 8561
(2017/12/12)
-
- Hydrothiolation of Alkenes and Alkynes Catalyzed by 3,4-Dimethyl-5-vinylthiazolium iodide and Poly(3,4-dimethyl-5-vinylthiazolium) iodide
-
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
-
p. 2476 - 2481
(2016/08/24)
-
- Decarbonylation of Salicylaldehyde Activated by p-Cymene Ruthenium(II) Dimer: Implication for Catalytic Alkyne Hydrothiolation
-
A stoichiometric C–H activation/decarbonylation of salicylaldehyde by [(η6-p-cymene)RuCl2]2gave a carbonyl derivative [(η6-p-cymene)RuCl(CO)(Ph-O)] (1) without the use of CO gas. A variety of polar phosphines were then incorporated into compound 1 to give new RuIIcationic catalysts, [(η6-p-cymene)Ru(CO)(Ph-O)L]BF4(2–8). These were used to catalyse the hydrothiolation of alkynes with a range of thiols in aqueous THF to give anti-Markovnikov E-linear vinyl sulfides in high yields.
- Modem, Sarangapani,Kankala, Shravankumar,Balaboina, Ramesh,Thirukovela, Narasimha Swamy,Jonnalagadda, Sreekantha B.,Vadde, Ravinder,Vasam, Chandra Sekhar
-
p. 4635 - 4642
(2016/09/28)
-
- Wittig–Horner mediated synthesis of 4-vinyl sulfide derivatives of pyrazoles
-
The synthesis of a series of 4-vinyl sulfide derivatives of 1,3-diarylpyrazoles, including their corresponding sulfoxides and sulfones, is reported. Access to the target vinyl sulfides was stereoselectively achieved, in moderate to good yields, by the n-BuLi-mediated Wittig–Horner reaction of 4-formylpyrazoles with arylthiophosphonates and α-chloroarylthiophosphonates in dimethoxyethane. Their oxidation with H2O2in AcOH and mCPBA in CH2Cl2afforded satisfactory yields of the expected vinyl sulfoxides and vinyl sulfones, respectively. Enrichment in the more stable isomers during both oxidation processes was detected and a plausible general mechanistic explanation was given to these observations.
- Padilha, Gustavo,Kaufman, Teodoro S.,Silveira, Claudio C.
-
p. 3349 - 3353
(2016/07/12)
-
- Preparation of a microporous organic polymer by the thiol-yne addition reaction and formation of Au nanoparticles inside the polymer
-
A microporous polymer with sulfide and thiol groups was synthesized using the thiol-yne reaction. Au nanoparticles were prepared by in situ reduction reaction inside the polymer and were found to be well dispersed. The Au-containing polymer showed catalytic activity in the reduction of 4-nitrophenol.
- Lee, Hyunpyo,Kim, Hyungwoo,Choi, Tae Jin,Park, Hyun Woo,Chang, Ji Young
-
supporting information
p. 9805 - 9808
(2015/06/16)
-
- Highly stereoselective anti-Markovnikov hydrothiolation of alkynes and electron-deficient alkenes by a supported Cu-NHC complex
-
A practical, efficient, and low-cost heterogeneous catalyst consisting of a Cu-NHC (N-heterocyclic carbene) complex grafted to SBA-15 silica for the catalytic hydrothiolation of alkynes and electron-deficient alkenes under mild reaction conditions has been developed. The heterogeneous catalyst displays higher activity and stereoselectivity to Z-anti-Markovnikov isomers compared with the homogeneous analog under otherwise identical reaction conditions. The catalytic system is applicable to a broad range of alkynes and thiols and is recyclable without significant loss in catalytic performance. High activity and perfect selectivity to alkyl sulfides formed by the addition of electron-deficient alkenes to various thiols catalyzed by the supported Cu-NHC complex were also realized. This journal is the Partner Organisations 2014.
- Yang, Yong,Rioux, Robert M.
-
p. 3916 - 3925
(2014/08/05)
-
- Amino acid and water-driven tunable green protocol to access S-S/C-S bonds via aerobic oxidative coupling and hydrothiolation
-
A green methodology utilizing a natural supplement such as l-arginine in conjunction with water and oxygen led to oxidative coupling of thiols into disulfides (S-S bond) whereas thiol-yne coupling to access vinyl sulfides (C-S bond) was facilitated in a nitrogen atmosphere. The tunable protocol offers several advantages such as low catalyst loading, high yields, clean reaction, no over-oxidation of the S-S bond besides being metal/base/waste-free. The synthesis of ubiquitous cystine and glutathione disulfide in the same catalytic system is an added advantage and the catalytic system has been recycled up to seven times. the Partner Organisations 2014.
- Shard, Amit,Kumar, Rajesh,Saima,Sharma, Nidhi,Sinha, Arun K.
-
p. 33399 - 33407
(2014/08/18)
-
- A recyclable biphasic system for stereoselective and easily handled hydrochalcogenations
-
Vinyl selenides and vinyl sulfides were prepared by hydrochalcogenation of alkynes with selenols and thiols generated in situ by the reduction of the corresponding diselenides and disulfides with elemental zinc in a biphasic acidic medium. The yields, ste
- Tidei, Caterina,Sancineto, Luca,Bagnoli, Luana,Battistelli, Benedetta,Marini, Francesca,Santi, Claudio
-
supporting information
p. 5968 - 5975
(2015/03/30)
-
- Regioselective hydrothiolation of alkynes by sulfonyl hydrazides using organic ionic base-Br?nsted acid
-
A practical and novel approach has been developed for the synthesis of vinyl sulfides by the reaction of sulfonyl hydrazides with aryl/ heteroarylacetylenes using a DBU-based ionic liquid. The system offers a new sulfur source for hydrothiolation and is endowed with green credentials.
- Singh, Rahul,Raghuvanshi, Dushyant Singh,Singh, Krishna Nand
-
supporting information
p. 4202 - 4205
(2013/09/12)
-
- Glycerol/CuI/Zn as a recyclable catalytic system for synthesis of vinyl sulfides and tellurides
-
A convenient approach to the Cu-catalyzed coupling of diphenyl disulfide and diphenyl ditelluride with vinyl bromides using a recyclable catalytic system and glycerol as a green solvent is described. This protocol was efficiently used in the preparation of vinyl sulfides and vinyl tellurides with a variety of substituents in good yields and stereoselectively. The solvent/catalyst system was directly reused for four cycles without loss of activity.
- Gon?alves, Lóren C.C.,Lima, David B.,Borba, Pedro M.Y.,Perin, Gelson,Alves, Diego,Jacob, Raquel G.,Lenard?o, Eder J.
-
p. 3475 - 3480
(2013/07/05)
-
- Regio- and stereoselective copper-catalyzed addition of aromatic and aliphatic thiols to terminal and internal nonactivated alkynes
-
The CuI-catalyzed regio- and stereoselective hydrothio-lation of terminal and internal alkynes affords (Z) - alkenylsulfides. The following isomerization of the Z-isomers into E-isomers catalyzed by CuI is described. Georg Thieme Verlag Stuttgart · New Yo
- Trostyanskaya, Inna G.,Beletskaya, Irina P.
-
experimental part
p. 535 - 540
(2012/04/10)
-
- Carbon dioxide mediated stereoselective copper-catalyzed reductive coupling of alkynes and thiols
-
A simple protocol for the stereoselective copper-catalyzed hydrothiolation of alkynes under a CO2 atmosphere has been developed. The stereoselectivity is determined by the presence/absence of a CO2 atmosphere. The reaction system is robust and utilizes inexpensive, readily available substrates. A cyclic alkene/carboxylate copper complex intermediate is proposed as the key step in determining the stereoselectivity, and an equivalent amount of water is found to play an active role as a proton donor.
- Nurhanna Riduan, Siti,Ying, Jackie Y.,Zhang, Yugen
-
supporting information; experimental part
p. 1780 - 1783
(2012/06/04)
-
- Synthesis of vinyl sulfides under base-free conditions using selenium ionic liquid
-
A very simple procedure is described for the efficient synthesis of vinyl sulfides by hydrothiolation of terminal alkynes using 1-n-butyl-3- methylimidazolium methylselenite, [bmim][SeO2(OCH3)]. The reaction proceeds cleanly under mi
- Thurow, Samuel,Ostosi, Naiana T.,Mendes, Samuel R.,Jacob, Raquel G.,Lenard?o, Eder J.
-
experimental part
p. 2651 - 2653
(2012/06/30)
-
- Ligand-controlled regioselectivity in the hydrothiolation of alkynes by rhodium N-heterocyclic carbene catalysts
-
Rh-N-heterocyclic carbene compounds [Rh(μ-Cl)(IPr)(ν2- olefin)]2 and RhCl(IPr)(py)(ν2-olefin) (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-carbene, py = pyridine, olefin = cyclooctene or ethylene) are highly active cata
- Di Giuseppe, Andrea,Castarlenas, Ricardo,Perez-Torrente, Jesus J.,Crucianelli, Marcello,Polo, Victor,Sancho, Rodrigo,Lahoz, Fernando J.,Oro, Luis A.
-
scheme or table
p. 8171 - 8183
(2012/07/13)
-
- Highly selective activation of vinyl C-S bonds over aryl C-S bonds in the Pd-catalyzed coupling of (E)-(β-trifluoromethyl)vinyldiphenylsulfonium salts: Preparation of trifluoromethylated alkenes and dienes
-
We describe the Suzuki coupling reaction of (E)-(β-trifluoromethyl) vinyldiphenylsulfonium salts with arylboronic acid. The highly efficient and selective reaction provides a useful and mild method for the synthesis of trifluoromethylated alkenes and dienes. Subsequent DFT studies showed that the oxidative addition transition state of the vinyl C-S bond is much more favorable (11.7 kcal mol-1) than that of the aryl C-S bond. Copyright
- Lin, Hao,Dong, Xicheng,Li, Yuxue,Shen, Qilong,Lu, Long
-
p. 4675 - 4679
(2012/10/08)
-
- Highly regio- and stereoselective hydrothiolation of acetylenes with thiols catalyzed by a well-defined supported Rh complex
-
Highly regio- and stereoselective hydrothiolation of a wide range of alkynes with various thiols was demonstrated in the presence of a well-defined Rh complex supported on mesoporous SBA-15 silica. The catalyst was easily recovered and reused several times without significant loss of activity or selectivity.
- Yang, Yong,Rioux, Robert M.
-
supporting information; experimental part
p. 6557 - 6559
(2011/06/28)
-
- Efficient copper-catalyzed s-vinylation of thiols with vinyl halides
-
The synthesis of vinyl sulfides through the coupling reaction of thiols with vinyl iodides, bromides, and chlorides is described. The thiols can couplewith aryl iodides in the presence of only 0.5mol% Cu2O without the need for an ancillary liga
- Kao, Hsin-Lun,Lee, Chin-Fa
-
supporting information; experimental part
p. 5204 - 5207
(2011/12/04)
-
- 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)
-
- Synthesis of vinyl sulfides by copper-catalyzed decarboxylative C-S cross-coupling
-
A novel method for the synthesis of vinyl sulfides by the decarboxylative cross-coupling of arylpropiolic acids with thiols using copper(I) salts as catalysts has been developed. In the presence of CuI and Cs2CO 3, a variety of thiols reacted with arylpropiolic acids to afford the corresponding vinyl sulfides in good to excellent yields with high stereoselectivity for Z-isomers.
- Ranjit, Sadananda,Duan, Zhongyu,Zhang, Pengfei,Liu, Xiaogang
-
supporting information; experimental part
p. 4134 - 4136
(2010/11/17)
-
- Rhodium(I) and iridium(I) complexes containing bidentate phosphine-imidazolyl donor ligands as catalysts for the hydroamination and hydrothiolation of alkynes
-
A series of novel cationic and neutral rhodium and iridium complexes containing bidentate phosphine-imidazolyl donor ligands of the general formulae [M(ImP)(COD)]BPh4 (M = Rh, ImP = ImP2, 3; ImP1a, 4a; ImP1b, 4b and M = Ir, ImP = ImP2, 5; ImP1a, 6a and ImP1b, 6b), [Ir(ImP)(CO)2]BPh 4 (ImP = ImP2, 7; ImP1a, 8a and ImP1b, 8b), [Rh(ImP1b)(CO) 2]BPh4 (10b) and [M(ImP)(CO)Cl] (M = Rh, ImP = ImP2, 11; ImP1b, 12 and M = Ir, ImP = ImP2, 13; ImP1b, 14) where COD = 1,5-cyclooctadiene, ImP2 = 1-methyl-2-[(2-(diphenylphosphino)ethyl]imidazole, 1; ImP1a = 1-methyl-2-[(diphenylphosphino)methyl]imidazole, 2a and ImP1b = 2-[(diisopropylphosphino)methyl]-1-methylimidazole, 2b were successfully synthesised. The solid state structures of 3, 6a, 11 and 12 were determined by single crystal X-ray diffraction analysis. A number of these complexes are effective as catalysts for the intramolecular hydroamination of 4-pentyn-1-amine to 2-methyl-1-pyrroline. The cationic complexes are significantly more effective than analogous neutral complexes. The cationic iridium complex 8b, containing the phosphine-imidazolyl ligand with the bulky isopropyl groups on the phosphorus donor, is more efficient than analogous complexes with the phenyl substituents on the phosphorus donor atom, 7 and 8a. The complexes 7-8b are also moderately effective in catalysing the addition of thiophenol to a range of terminal alkynes. In contrast to the hydroamination reaction, placement of the isopropyl group on the phosphorus donor leads to a decrease in the reactivity of the resulting metal complexes as catalysts for the hydrothiolation reaction.
- Field, Leslie D.,Messerle, Barbara A.,Vuong, Khuong Q.,Turner, Peter
-
scheme or table
p. 3599 - 3614
(2009/09/07)
-
- Water-promoted regioselective hydrothiolation of alkynes
-
Water promotes hydrothiolation of unactivated alkynes efficiently without any catalyst or additive. The reaction at room temperature furnishes vinyl sulfides with high regioselectivity via anti-Markovnikov addition. The terminal al- kynes provide dithiola
- Bhadra, Sukalyan,Ranu, Brindaban C.
-
experimental part
p. 1605 - 1609
(2010/04/03)
-
- Cesium Salt-Catalyzed Addition of Diphenyl Dichalcogenides to Alkynes: Selective Synthesis of Bis- and Mono(phenylchalcogeno)alkenes
-
A cesium salt has a unique catalytic ability for the reaction of alkynes with diphenyl dichalcogenides. When the diphenyl dichalcogenides, such as the disulfide, diselenide, or ditelluride, were allowed to react with alkynes in the presence of a catalytic
- Nishiyama, Yutaka,Ohnishi, Haruko,Koguma, Yuya
-
experimental part
p. 1170 - 1174
(2009/12/25)
-
- Reductive addition of the benzenethiyl radical to alkynes by amine-mediated single electron transfer reaction to diphenyl disulfide
-
Hydrothiolation of alkynes proceeds with diphenyl disulfide and tripropylamine. Amine-mediated single electron transfer to diphenyl disulfide can be proposed for the reaction mechanism. Applications of the method to radical cyclizations of eneyne compound
- Taniguchi, Tsuyoshi,Fujii, Tatsuya,Ldota, Atsushi,Lshibashi, Hiroyuki
-
supporting information; experimental part
p. 3298 - 3301
(2009/12/01)
-
- Zinc-mediated palladium-catalyzed formation of carbon-sulfur bonds
-
(Chemical Equation Presented) A catalytic amount of zinc chloride in combination with a palladium catalyst ligated by a monodentate phosphine allows the coupling of aryl and alkyl thiols with aryl bromides in high yields. The addition of zinc chloride to a palladium catalyst system that reportedly failed to promote sulfide formation allows this once ineffective catalyst system to provide the sulfide product in good yield. This paper describes a high-yielding and general monodentate phosphine-ligated palladium catalyst for biaryl and alkyl aryl sulfide formation.
- Eichman, Chad C.,Stambuli, James P.
-
supporting information; experimental part
p. 4005 - 4008
(2009/10/02)
-
- Straightforward and highly efficient catalyst-free regioselective reaction of thiol to β-nitrostyrene: a concise synthesis of vinyl sulfide and nitro sulfide
-
Under catalyst-free reaction conditions, solvent-mediated addition of thiol 2 to β-nitrostyrene 1 proceeded with regioselective control to afford either adduct 3 or vinyl sulfide 4 in good to excellent yield. Thermodynamic and autocatalytic reaction mecha
- Chu, Cheng-Ming,Tu, Zhijay,Wu, Pohsi,Wang, Chieh-Chieh,Liu, Ju-Tsung,Kuo, Chun-Wei,Shin, Yu-Hsuan,Yao, Ching-Fa
-
scheme or table
p. 3878 - 3885
(2009/09/30)
-
- Synthesis of aryl sulfides by decarboxylative C-S cross-couplings
-
A study was conducted to demonstrate the transition-metal-catalyzed synthesis of aryl sulfides by decarboxylative C-S cross-couplings. Coupling reaction of 2-nitrobenzoic acid with 1-octanethiol were carried in the presence of different combinations of tr
- Duan, Zhongyu,Ranjit, Sadananda,Zhang, Pengfei,Liu, Xiaogang
-
supporting information; experimental part
p. 3666 - 3669
(2009/12/07)
-
- Mild Copper(I) iodide/β-keto ester catalyzed coupling reactions of styryl bromides with phenols, thiophenols, and imidazoles
-
An efficient and mild vinylation of O-, S-, and N-nucleophiles is reported. Copper(I) iodide/ethyl 2-oxocyclohexanecarboxylate is used as the catalytic system. The protocol tolerates a broad range of functional groups on the substrates, and gives the corr
- Bao, Weiliang,Liu, Yunyun,Lv, Xin
-
experimental part
p. 1911 - 1917
(2009/04/04)
-
- Synthesis of vinyl sulfides via hydrothiolation of alkynes using Al2O3/KF under solvent-free conditions
-
We present here a clean, solvent-free hydrothiolation of alkynes using solid supported catalyst (Al2O3/KF). This efficient and improved method selectively furnishes the corresponding anti-Markovnikov vinyl sulfides in good to excellent yields. The method is applicable for aliphatic and aromatic thiols and the catalytic system can be re-used up to two times without previous treatment and with comparable activity.
- Silva, Márcio S.,Lara, Renata G.,Marczewski, Júnior M.,Jacob, Raquel G.,Lenard?o, Eder J.,Perin, Gelson
-
p. 1927 - 1930
(2008/09/19)
-
- Ionic liquid promoted regio- And stereoselective addition of thiols to alkynes and alkenes under organic solvent free condition - A green reaction
-
A simple ionic liquid, l-methyl-3-pentylimidazolium fluoroborate, [pmIm]BF4, promotes anti-Markovnikov addition of thiols to alkynes providing (Z)- and (E)-vinyl sulfides stereoselectively. The addition of thiols to alkenes in presence of another ionic liquid, [pmim]Br proceeds through anti-Markovnikov manner, whereas the addition to vinyl ethers and acetates occurs at more electrophilic C-2 position adjacent to oxygen. The products are obtained in high yields.
- Ranu, Brindaban C.,Chattopadhyay, Kalicharan,Ghosh, Sudip,Jana, Ranjan
-
experimental part
p. 1199 - 1204
(2009/12/31)
-
- Hydroalumination of thioacetylenes: A versatile generation and reactions of α-aluminate sulfides intermediates
-
Hydroalumination of thioacetylenes using DIBAL-H and lithium di-(isobutyl)-n-(butyl)-aluminate hydride (Zweifel's reagent), followed by addition of water, furnished exclusively the (Z)- and (E)-vinyl sulfides, respectively. The regio- and stereochemistry
- Guerrero Jr.,Dabdoub,Marques,Wosch,Baroni,Ferreira
-
experimental part
p. 4379 - 4394
(2009/04/11)
-
- A simple and general preparation of vinylic sulfides, selenides and tellurides
-
A general method for the synthesis of vinylic chalcogenides by nucleophilic and Ni-catalyzed vinylic substitution on vinylic halides by phenyl chalcogenolates is described. The reactions were regio and stereoselective for the nickel catalyzed substitution
- Silveira, Claudio C.,Santos, Paulo Cesar S.,Mendes, Samuel R.,Braga, Antonio L.
-
scheme or table
p. 3787 - 3790
(2009/04/06)
-
- Hydrothiolation of terminal alkynes with diaryl disulfides and diphenyl diselenide: selective synthesis of (Z)-1-alkenyl sulfides and selenides
-
A simple, stereoselective and efficient method for the hydrothiolation of terminal alkynes with diaryl disulfides and diphenyl diselenide has been developed. In the presence of CuI, rongalite, and Cs2CO3, a variety of disulfides underwent the reaction of terminal alkynes stereoselectively to afford the corresponding (Z)-1-alkenyl sulfides in moderate to excellent yields. It is noteworthy that hydroselenations of 1,2-diphenyldiselane with alkynes are also conducted smoothly to afford (Z)-1-alkenyl selenides in good yields under the standard conditions.
- Wang, Zhang-Lin,Tang, Ri-Yuan,Luo, Pei-Song,Deng, Chen-Liang,Zhong, Ping,Li, Jin-Heng
-
p. 10670 - 10675
(2008/12/23)
-
- Mild, efficient and highly stereoselective synthesis of (Z)-vinyl chalcogenides from vinyl bromides catalyzed by copper(I) in ionic liquids based on amino acids
-
A method for the synthesis of (Z)-vinyl chalcogenides by the coupling of vinyl bromides with thiols or diphenyl diselenide using copper(l) salts as catalysts in ionic liquids based on amino acids is reported. The desired vinyl chalcogenides were obtained
- Wang, Zhiming,Mo, Hanjie,Bao, Weiliang
-
-