- Acid-Mediated Sulfonylthiolation of Arenes via Selective Activation of SS-Morpholino Dithiosulfonate
-
A trifluoroacetic-acid-mediated desulfurilative sulfonylthiolation of arenes using SS-morpholino dithiosulfonate is described. This system is based on selective activation of the morpholino group over the tosyl group of the doubly transformable sulfur surrogate. Mechanistic studies suggested that the reaction proceeds through electrophilic aromatic substitution followed by sulfur extrusion. The wide substrate scope of this reaction and the transformability of the resulting thiosulfonates enable expeditious access to divergent multifunctionalized sulfides.
- Kanemoto, Kazuya,Furuhashi, Koudai,Morita, Yoshitsugu,Komatsu, Teruyuki,Fukuzawa, Shin-Ichi
-
-
Read Online
- Nickel-Catalyzed Difunctionalization of Alkynyl Bromides with Thiosulfonates and N -Arylthio Succinimides: A Convenient Synthesis of 1,2-Thiosulfonylethenes and 1,1-Dithioethenes
-
An efficient nickel-catalyzed vicinal thiosulfonylation of 1-bromoalkynes with thiosulfonates in the presence of cesium carbonate is described. An operationally simple and highly regioselective atom transfer radical addition (ATRA) of alkynyl bromides provides a wide range of (E)-1,2-thiosulfonylethenes (α-aryl-β-thioarylvinyl sulfones) in moderate to high yields. The extensive substrate scope of both alkynyl bromides and thiosulfonates is explored with a broad range of functional groups. Indole-derived 1,1-bromoalkenes were also successfully explored in this 1,2-thiosulfonylation process. Moreover, the nickel-catalyzed geminal -dithiolation of alkynyl bromides with N -arylthio succinimides provides 1,1-dithioalkenes in high yields. The present protocol is reliable on gram scale, and a sequential one-pot bromination and thiosulfonylation of phenylacetylene is achieved in a scale-up synthesis. Following control experiments, a plausible mechanism is proposed to rationalize the experimental outcome and the vicinal thio-sulfonylation.
- Kumari, Arram Haritha,Kumar, Jangam Jagadesh,Krishna, Gamidi Rama,Reddy, Raju Jannapu
-
supporting information
p. 2850 - 2864
(2021/05/18)
-
- Atom transfer radical addition to styrenes with thiosulfonates enabled by synergetic copper/photoredox catalysis
-
A synergetic copper/photoredox catalyzed ATRA of styrenes and thiosulfonates is developed. Besides aryl ethylenes, the challenging α-substituted styrenes were employed to construct the benzylic quaternary carbon centers. Owing to the mild conditions as well as the high level of substrate compability, this ATRA could be applied to derivatize bioactive natural products in late stage, and to install fluorophores across alkenes. The mechanistic studies reveal sulfonyl radicals as the key intermediate in the transformation.
- Zhou, Xin,Peng, Zhiyuan,Wang, Peng George,Liu, Qingchao,Jia, Tiezheng
-
supporting information
p. 1054 - 1059
(2021/02/01)
-
- TFA promoted multi-component reaction of aryldiazonium with sodium metabisulphite and thiols: Construction of thiosulfonate under transition-metal free conditions
-
A TFA promoted multi-component reaction of aryldiazonium with sodium metabisulphite and thiols to construct thiosulfonates under transition-metal free conditions is reported. The thiosulfonates were isolated in good yields with broad tolerance of function
- Huang, Cheng-Mi,Li, Jian,Wang, Shun-Yi,Ji, Shun-Jun
-
supporting information
p. 1923 - 1926
(2020/01/13)
-
- Organocatalytic Transformation of Aldehydes to Thioesters with Visible Light
-
A metal- and oxidant-free catalytic method for accessing structurally diverse thioesters from readily accessible, widespread aldehydes, is described. A strategy of a simple organic 9,10-phenanthrenequinone-promoted hydrogen atom transfer (HAT) with visible light was successfully implemented to selectively generate acyl radicals without inducing crossover reactivity of thioester products. The preparative power of the method was demonstrated by broad substrate scope and wide functional group tolerance, and enabled the late-stage modification of complex structures, which are difficult to achieve with the existing protocols.
- Zhang, Yueteng,Ji, Peng,Hu, Wenbo,Wei, Yongyi,Huang, He,Wang, Wei
-
supporting information
p. 8225 - 8228
(2019/07/16)
-
- Electrochemical Oxidative Cross-Coupling Reaction to Access Unsymmetrical Thiosulfonates and Selenosulfonates
-
The electrochemical oxidative cross-dehydrogenative coupling of arylsulfinic acids with thiophenols was achieved via a radical process. A wide range of arylsulfinic acids and substituted thiophenols were found to be tolerated, providing unsymmetrical thio
- Zhang, Xiaofeng,Cui, Ting,Zhang, Yanghao,Gu, Weijin,Liu, Ping,Sun, Peipei
-
p. 2014 - 2019
(2019/03/26)
-
- Unsymmetrical Organotrisulfide Formation via Low-Temperature Disulfanyl Anion Transfer to an Organothiosulfonate
-
New methodology is presented for the formation of unsymmetrical organotrisulfides in a high yield and purity, relatively free of polysulfide byproducts. The highlight of the method is the low-temperature (-78 °C) deprotection of a disulfanyl acetate with sodium methoxide in THF to form a disulfanyl anion, which reacts rapidly in situ with an organothiosulfonate (S-aryl or S-alkyl) within 30 seconds followed by quenching. The discovery of these new reaction conditions together with the relative greenness of the chemistry overall makes for an efficient protocol, from which a range of organotrisulfides covering aliphatic, aromatic, as well as cysteine and sugar groups can be accessed in a high yield and purity.
- Ali, Doaa,Hunter, Roger,De Doncker, Stephen,Rees-Jones, Sophie C. M.,Kaschula, Catherine H.
-
p. 2862 - 2869
(2019/03/23)
-
- Selective Ortho Thiolation Enabled by Tuning the Ancillary Ligand in Palladium/Norbornene Catalysis
-
Site-selective introduction of a sulfur group into aromatic compounds is essential and useful in organic, material, and pharmaceutical chemistry. A palladium/norbornene-catalyzed chemoselective ortho thiolation of aryl halides was reported. The selectivit
- Cai, Wenqiang,Gu, Zhenhua
-
supporting information
p. 3204 - 3209
(2019/05/01)
-
- PTAB mediated open air synthesis of sulfonamides, thiosulfonates and symmetrical disulfanes
-
A facile methodology has been described which has successfully simplified the generation of sulfonamides, thiosulfonates and symmetric disulfanes. This “trio” of reactions occur in an open air metal free atmosphere and has also been scaled up to grams making it suitable for commercialization. The reactions also have been successfully carried out with asymmetric variants, thus contributing to the chiral pool. The user friendly “trio” enables easy generation of these versatile sulfur analogues and the reaction condition employed depict an economic outline.
- Sarkar, Debayan,Ghosh, Manoj Kumar,Rout, Nilendri
-
p. 2360 - 2364
(2018/05/24)
-
- H2O2-mediated metal-free protocol towards unsymmetrical thiosulfonates from sulfonyl hydrazides and disulfides in PEG-400
-
A green and practical protocol between sulfonyl hydrazides and disulfides is herein reported for the synthesis of unsymmetrical thiosulfonates with the assistance of H2O2 in PEG-400, releasing N2 and H2O as the byproducts. The efficient and compatible process was considered to take place in the absence of metallic catalysts through a radical mechanism as determined by EPR analysis.
- Peng, Zhihong,Zheng, Xiao,Zhang, Yingjun,An, Delie,Dong, Wanrong
-
supporting information
p. 1760 - 1764
(2018/04/30)
-
- Modified conditions for copper-catalyzed ipso-thiolation of arylboronic acid esters with thiosulfonates
-
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
-
supporting information
p. 85 - 88
(2018/01/26)
-
- Rhodium-catalyzed odorless synthesis of diaryl sulfides from borylarenes and: S -aryl thiosulfonates
-
Various diaryl sulfides, including heteroaryl- and nitrogen-containing sulfides, have been efficiently prepared by rhodium-catalyzed odorless deborylative arylthiolation of organoborons with S-aryl thiosulfonates. The ready availability of starting materials and further transformation of sulfides have rendered a diverse range of organosulfur compounds easily accessible.
- Kanemoto, Kazuya,Sugimura, Yasuyuki,Shimizu, Shigeomi,Yoshida, Suguru,Hosoya, Takamitsu
-
p. 10640 - 10643
(2017/10/06)
-
- Oxidative coupling of dichalcogenides with sodium sulfinates via copper-catalyzed cleavage of s-s and se-se bonds
-
A copper-catalyzed sulfonylation of disulfides was achieved using sodium sulfinates in air. The reaction formed various sulfur-sulfone bonds efficiently and afforded thiosulfonates in good yields. Selenosulfonates could also be prepared with this procedure. Furthermore, both chalcogenide groups on the dichalcogenides were available in these reactions.
- Taniguchi, Nobukazu
-
p. 1764 - 1770
(2015/02/19)
-
- Synthesis of S-Aryl arenethiosulfonates from N,N-Di(arenesulfonyl) hydrazines: Reduction of sulfonyl chlorides with an organic reagent
-
N,N-Di(arenesulfonyl)-N′,N′-dimethyl-hydrazines, readily prepared from arenesulfonyl chlorides and N,N-dimethylhydrazine, were heated at 120°C in chlorobenzene to give S-aryl arenethiosulfonates, ArSSO 2Ar, in good yields.
- Iwata, Satoshi,Senoo, Masato,Hata, Takeshi,Urabe, Hirokazu
-
p. 336 - 344
(2013/08/23)
-
- Sc(OTf)3-catalyzed synthesis of thiosulfonates in ionic liquid-water
-
The first example of Sc(OTf)3-catalyzed sulfenylation of sodium sulfinates with N-(organothio)succinimides in ionic liquids (ILs) and water cosolvent system was developed, achieving thiosulfonates in moderate to excellent yields. Additionally, Sc(OTf)3/ILs could be recovered easily after the reactions and reused without a significant loss in the catalytic activity. Thus, the present protocol represents an interesting complement to known methods for thiosulfonates synthesis.
- Liang, Gaigai,Chen, Jing,Chen, Jiali,Li, Wanmei,Chen, Jiuxi,Wu, Huayue
-
supporting information
p. 6768 - 6770
(2013/01/15)
-
- Regioselective cobalt-catalyzed addition of sulfides to unactivated alkenes
-
A novel method to synthesize tertiary alkyl/aryl sulfides in a mild and regioselective manner from unactivated alkenes using cobalt catalysis is described. The methodology is compatible with sensitive functionalities and is successful with several different types of alkenes and sulfides.
- Girijavallabhan, Vinay,Alvarez, Carmen,Njoroge, F. George
-
experimental part
p. 6442 - 6446
(2011/09/16)
-
- New and facile synthesis of thiosulfonates from sulfinate/disulfide/I2 system
-
Thiosulfonates were prepared by the iodine oxidative sulfenylation of sulfinates with various disulfides in good yields both in the presence and absence of solvent. One of the important biological applications of sulfenylation is the reaction of cyclic disulfides.
- Fujiki, Kiyoko,Tanifuji, Naoki,Sasaki, Yohei,Yokoyama, Taku
-
p. 343 - 348
(2007/10/03)
-
- S-TOSYLSULFENAMIDES, NEW ELECTROPHILIC SULFOSULFENYLATING AGENTS
-
A method has been developed for the synthesis of thiosulfonates by the electrophilic substitution addition of S-tosylsulfenamides to olefins or their electrophilic in aromatic systems.SO3, Py*SO3, and BF3*Et2O were used as activators.The addition of S-tos
- Zefirov, N.S.,Zyk, N.V.,Kutateladze, A.G.,Beloglazkina, E.K.
-
p. 2296 - 2301
(2007/10/02)
-
- THIOSULFONIC S-ESTERS - 5. MECHANISTIC ASPECTS OF THE REACTION WITH CHLOROTRIMETHYLSILANE AND SODIUM IODIDE
-
Thiosulfonic S-esters (1) are readily converted to disulfides (2) by chlorotrimethylsilane and sodium iodide.The reaction is shown to proceed through a complex mechanism, and more than one conversion pathway to disulfides must be considered.Evidence is presented for several S-S bond cleavage and reformation reactions involved in the conversion.In view of these results, the mechanistic interpretations proposed for already known reactions of various sulfur compounds with either chlorotrimethylsilane-iodide or iodotrimethylsilane should probably be revised.The behaviour of other reducing agents of thiosulfonates (1) to disulfides (2) was also checked.
- Caputo, Romualdo,Ferreri, Carla,Palumbo, Giovanni
-
p. 5377 - 5384
(2007/10/02)
-