- 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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- Nickel-Catalyzed Inter- and Intramolecular Aryl Thioether Metathesis by Reversible Arylation
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A nickel-catalyzed aryl thioether metathesis has been developed to access high-value thioethers. 1,2-Bis(dicyclohexylphosphino)ethane (dcype) is essential to promote this highly functional-group-tolerant reaction. Furthermore, synthetically challenging macrocycles could be obtained in good yield in an unusual example of ring-closing metathesis that does not involve alkene bonds. In-depth organometallic studies support a reversible Ni0/NiII pathway to product formation. Overall, this work not only provides a more sustainable alternative to previous catalytic systems based on Pd, but also presents new applications and mechanistic information that are highly relevant to the further development and application of unusual single-bond metathesis reactions.
- Delcaillau, Tristan,Bismuto, Alessandro,Lian, Zhong,Morandi, Bill
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supporting information
p. 2110 - 2114
(2019/12/24)
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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 9; 20; 21
(2018/09/28)
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- N-heterocyclic carbene-catalyzed regio- and stereoselective hydrothiolation reaction of alkynes
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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
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supporting information
p. 1838 - 1846
(2018/06/25)
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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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- 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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- Indium(iii) catalysed substrate selective hydrothiolation of terminal alkynes
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In(OTf)3 is reported as the first catalyst having the ability to selectively catalyse both Markovnikov and anti-Markovnikov hydrothiolation of terminal alkynes under identical reaction conditions depending upon the nature of the thiol employed.
- Sarma, Rupam,Rajesh, Nimmakuri,Prajapati, Dipak
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supporting information; experimental part
p. 4014 - 4016
(2012/06/01)
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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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- 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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- Synthesis of aryl sulfides by decarboxylative C-S cross-couplings
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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
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supporting information; experimental part
p. 3666 - 3669
(2009/12/07)
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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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- Stereo-recognizing transformation of (E)-alkenyl halides into sulfides catalyzed by nickel(0) triethyl phosphite complex
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(E)-Alkenyl halides were transformed into (E)-alkenyl sulfides by the nickel(0) triethyl phosphite complex-catalyzed reaction with thiols, whereas (Z)-alkenyl halides gave alkynes under the same reaction conditions. Aryl halides were also transformed into aryl sulfides using the same reagent system.
- Yatsumonji, Yasutaka,Okada, Orie,Tsubouchi, Akira,Takeda, Takeshi
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p. 9981 - 9987
(2007/10/03)
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- Copper-catalyzed synthesis of vinyl sulfides
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(Chemical Equation Presented) We report a method for the synthesis of vinyl sulfides using the soluble copper(I) catalyst [Cu(phen)(PPh3) 2]NO3. The desired vinyl sulfides are obtained in good to excellent yields, with retention of stereochemistry. This protocol tolerates a wide variety of functional groups or substrates, is palladium-free, and does not require the use of expensive or air-sensitive additives.
- Bates, Craig G.,Saejueng, Pranorm,Doherty, Michael Q.,Venkataraman
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p. 5005 - 5008
(2007/10/03)
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