- Forging C?S(Se) Bonds by Nickel-catalyzed Decarbonylation of Carboxylic Acid and Cleavage of Aryl Dichalcogenides
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A nickel-catalyzed decarbonylation of carboxylic acids cross-coupling protocol has been developed for the straightforward C?S(Se) bond formation. This reaction is promoted by a commercially-available, user-friendly, inexpensive, air and moisture-stable nickel precatalyst. Various carboxylic acids and a wide range of aryl dichalcogenide substrates were tolerated in this process which afforded products in good to excellent yields. In addition, the present reaction can be conducted on gram scale in good yield.
- Zhou, Jing-Ya,Zhu, Yong-Ming
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p. 2452 - 2461
(2021/06/28)
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- Electrophilic Vinylation of Thiols under Mild and Transition Metal-Free Conditions
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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
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supporting information
p. 15512 - 15516
(2020/06/23)
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- A Simplified Protocol for the Stereospecific Nickel-Catalyzed C-S Vinylation Using NiX 2 Salts and Alkyl Phosphites
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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
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p. 311 - 319
(2019/12/28)
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- Anti-Markovnikov stereoselective hydroamination and hydrothiolation of (hetero)aromatic alkynes using a metal-free cyclic trimeric phosphazene base
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Hydroamination and hydrothiolation are the most efficient and completely atom-economical process to construct important enamine and vinyl sulfide intermediates in pharmaceutical and organic chemistry. The cyclic trimeric phosphazene base (CTPB) showed gre
- Zhao, Na,Lin, Chengdong,Wen, Lirong,Li, Zhibo
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p. 3432 - 3440
(2019/05/15)
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- Acid/Phosphide-Induced Radical Route to Alkyl and Alkenyl Sulfides and Phosphonothioates from Sodium Arylsulfinates in Water
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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
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p. 382 - 389
(2017/04/26)
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- Stereoselective Synthesis of Alkenyl Silanes, Sulfones, Phosphine Oxides, and Nitroolefins by Radical C-S Bond Cleavage of Arylalkenyl Sulfides
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A radical-mediated approach has been introduced for the C-S bond activation of arylalkenyl sulfides. The protocol provides an efficient approach for the generation of various alkenes including alkenyl silanes, sulfones, phosphine oxides, and nitroolefins. In most cases, these radical substitutions are performed under metal-free conditions with stereospecificity.
- Lin, Ya-mei,Lu, Guo-ping,Wang, Rong-kang,Yi, Wen-bin
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supporting information
p. 1100 - 1103
(2017/03/15)
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- Regioselective hydrothiolation of terminal acetylene catalyzed by magnetite (Fe3O4) nanoparticles
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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.
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supporting information
p. 291 - 298
(2017/02/10)
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- Decarbonylation of Salicylaldehyde Activated by p-Cymene Ruthenium(II) Dimer: Implication for Catalytic Alkyne Hydrothiolation
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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
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p. 4635 - 4642
(2016/09/28)
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- Tuning the stereoelectronic properties of 1-sulfanylhex-1-enitols for the sequential stereoselective synthesis of 2-deoxy-2-iodo-β- d -allopyranosides
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The preparation of challenging 2-deoxy-2-iodo-β-d-allo precursors of 2-deoxy-β-d-ribo-hexopyranosyl units and other analogues is reported using a robust olefination-cyclization-glycosylation sequence. Here, we particularly focus on tuning the stereoelectronic properties of the alkenyl sulfides intermediates in order to improve the diastereoselectivity of the cyclization step and, hence, the efficiency of the overall transformation. Phosphine oxides with the general formula Ph2P(O)CH2SR (R = t-Bu, Cy, p-MeOPh, 2,6-di-ClPh, and 2,6-di-MePh) were easily synthesized and subsequently used in the olefination reaction with 2,3,5-tri-O-benzyl-d-ribose and -d-arabinose. The corresponding sugar-derived alkenyl sulfides were submitted to a 6-endo [I+]-induced cyclization, and the resulting 2-deoxy-2-iodohexopyranosyl-1-thioglycosides were used as glycosyl donors for the stereoselective synthesis of 2-deoxy-2-iodohexopyranosyl glycosides. Among the different S-groups studied, t-Bu derivative was the best performer for the synthesis of cholesteryl 2-deoxy-2-iodomannopyranosides, whereas for the synthesis of 2-deoxy-2-iodoallopyranosides none of the derivatives here studied proved superior to the phenyl analogue previously described. Glycosylation of cholesterol with different d-allo and d-manno derivatives produced 2-deoxy-2-iodoglycosides with stereoselectivities in the same order in each case, reinforcing the involvement of an oxocarbenium ion as the common intermediate of this crucial glycosylation step.
- K?vér, Andrea,Boutureira, Omar,Matheu, M. Isabel,Díaz, Yolanda,Castillón, Sergio
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p. 3060 - 3068
(2014/05/06)
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- Highly stereoselective anti-Markovnikov hydrothiolation of alkynes and electron-deficient alkenes by a supported Cu-NHC complex
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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.
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p. 3916 - 3925
(2014/08/05)
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- Glycerol/CuI/Zn as a recyclable catalytic system for synthesis of vinyl sulfides and tellurides
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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.
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p. 3475 - 3480
(2013/07/05)
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- Stereoselective formation of Z- or E-vinyl thioethers from arylthiols and acetylenes under transition-metal-free conditions
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Vinyl sulfide formation with good yield and high regio- and stereoselectivities from thiols and acetylenes under transition-metal-free conditions is described. Potassium phosphate was used as an effective additive to enhance the reaction yield and selecti
- Liao, Yunfeng,Chen, Shanping,Jiang, Pengcheng,Qi, Hongrui,Deng, Guo-Jun
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p. 6878 - 6885
(2013/11/06)
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- Regioselective hydrothiolation of alkynes by sulfonyl hydrazides using organic ionic base-Br?nsted acid
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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
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supporting information
p. 4202 - 4205
(2013/09/12)
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- Carbon dioxide mediated stereoselective copper-catalyzed reductive coupling of alkynes and thiols
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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
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supporting information; experimental part
p. 1780 - 1783
(2012/06/04)
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- Alkyne hydrothiolation catalyzed by a dichlorobis(aminophosphine) complex of palladium: Selective formation of cis-configured vinyl thioethers
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Cis all round: Dichlorobis[1-(dicyclohexylphosphanyl)piperidine]palladium, [(P{(NC5H10)(C6H11) 2})2Pd(Cl)2], is a highly efficient alkyne hydrothiolation catalyst and the first generally applicable system that selectively generates cis-configured anti-Markovnikov adducts in excellent yields within only a few minutes at 120 °C in the presence of only 0.05 mol % of the catalyst (see scheme).
- Gerber, Roman,Frech, Christian M.
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scheme or table
p. 8901 - 8905
(2012/09/25)
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- Highly regio- and stereoselective hydrothiolation of acetylenes with thiols catalyzed by a well-defined supported Rh complex
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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.
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supporting information; experimental part
p. 6557 - 6559
(2011/06/28)
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- Lanthanum-catalyzed stereoselective synthesis of vinyl sulfides and selenides
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Lanthanum oxide/TMEDA-catalyzed cross-coupling of vinyl halides with thiols/diphenyl diselenide in anhydrous DMSO and KOH is reported. Utilizing this protocol various vinyl sulfides and selenides were synthesized in excellent yields with retention of the stereochemistry. The catalyst was recyclable.
- Reddy, V. Prakash,Swapna,Kumar, A. Vijay,Rao, K. Rama
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experimental part
p. 293 - 296
(2010/03/26)
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- MnCl2·4H2O-catalyzed potential protocol for the synthesis of aryl/vinyl sulfides
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MnCl2 · 4H2O is described as an efficient catalytic system for the cross coupling of aryl/vinyl halides with thiols using KOH as base and DMSO as solvent. By using this new catalytic system various aryl/vinyl sulfides were synthesize
- Bandaru, Madhav,Sabbavarpu, Narayana Murthy,Katla, Ramesh,Yadavalli, Venkata Durga Nageswar
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supporting information; experimental part
p. 1149 - 1151
(2011/02/28)
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- Synthesis of vinyl sulfides by copper-catalyzed decarboxylative C-S cross-coupling
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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
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supporting information; experimental part
p. 4134 - 4136
(2010/11/17)
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- Recyclable nano copper oxide catalyzed stereoselective synthesis of vinyl sulfides under ligand-free conditions
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A simple and efficient protocol for the cross-coupling of vinyl halides with thiols catalyzed by recyclable CuO nanoparticles under ligand-free conditions is reported. This methodology results in the synthesis of a variety of vinyl sulfides in excellent y
- Reddy, Vutukuri Prakash,Swapna, Kokkirala,Kumar, Akkilagunta Vijay,Rao, Kakulapati Rama
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experimental part
p. 2783 - 2788
(2010/03/03)
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- Straightforward and highly efficient catalyst-free regioselective reaction of thiol to β-nitrostyrene: a concise synthesis of vinyl sulfide and nitro sulfide
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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
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scheme or table
p. 3878 - 3885
(2009/09/30)
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- Stereoselective synthesis of E-vinyl sulfides from alkynes in water under neutral conditions using β-cyclodextrin
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This is the first example of stereoselective synthesis of E-vinyl sulfides in water in excellent yields by hydrothiolation of aromatic alkynes with thiophenols by anti-Markonikov addition in the presence of β-cyclodextrin. This protocol tolerates a wide v
- Sridhar,Surendra,Srilakshmi Krishnaveni,Srinivas,Rama Rao
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p. 3495 - 3497
(2007/10/03)
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- Radical Addition to Isonitriles: A Route to Polyfunctionalized Alkenes through a Novel Three-Component Radical Cascade Reaction
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The reaction of aromatic disulfides, alkynes, and isonitriles under photolytic conditions affords polyfunctionalized alkenes - β-arylthio-substituted acrylamides or acrylonitriles - in fair yields through a novel three-component radical cascade reaction. The procedure entails addition of a sulfanyl radical to the alkyne followed by attack of the resulting vinyl radical to the isonitrile. A fast reaction, e.g., scavenging by a nitro derivative or β-fragmentation, is necessary in order to trap the final imidoyl radical, since addition of vinyl radicals to isonitriles seems to be a reversible process. The stereochemistry of the reaction is discussed, particularly with respect to the stereochemical outcome of related hydrogen abstraction reactions by the same vinyl radicals. The lower or even inverted preference for either geometrical isomer observed in our cases with respect to that encountered in hydrogen abstraction reactions is explained in terms of transition-state interactions and/or isomerization of the final imidoyl radical. The latter possibility is supported by semiempirical calculations, which show that the spin distribution in the imidoyl radical can allow rotation of the adjacent carbon - carbon double bond prior to β-fragmentation.
- Leardini, Rino,Nanni, Daniele,Zanardi, Giuseppe
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p. 2763 - 2772
(2007/10/03)
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