- Temperature-Controlled Chemoselective Synthesis of Thiosulfonates and Thiocyanates: Novel Reactivity of KXCN (X=S, Se) towards Organosulfonyl Chlorides
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An efficient chemoselective protocol has been developed for the synthesis of thiosulfonates and thiocyanates by employing cost effective and commercially available organosulfonyl chlorides with potassium thio-/selenocyanate. The strategy offered the thiosulfonates and thiocyanates selectively by tuning the equivalents of KSeCN and optimizing the reaction temperature. On the other hand, thiosulfonates were obtained as sole products when organosulfonyl chlorides were treated with KSCN. Furthermore, the syntheses of diarylthioethers and aryl(heteroaryl) thioethers were carried out as a part of synthetic application of newly prepared arylthiocyanates.
- Kalaramna, Pratibha,Goswami, Avijit
-
supporting information
p. 5359 - 5366
(2021/10/25)
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- Synthesis of Thio-/Selenopyrrolines via SnCl4-Catalyzed (3+2)-Cycloadditions of Donor-Acceptor Cyclopropanes with Thio-/Selenocyanates
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A straightforward protocol has been developed to access thio-/selenopyrrolines through a (3+2)-cycloaddition of aryl thio-/selenocyanates with donor-acceptor cyclopropanes (DACs) in the presence of SnCl4 as a Lewis acid catalyst. Further, good chemoselectivity was observed when DACs were treated with 3-cyano phenyl thiocyanate. These results suggest that thiocyanate is more reactive than nitrile moiety in such (3+2)-cycloaddition reactions.
- Ali, Shamsad,Goswami, Avijit,Kalaramna, Pratibha,Singh, Prasoon Raj
-
supporting information
p. 4683 - 4689
(2021/09/10)
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- Straightforward Access to Thiocyanates via Dealkylative Cyanation of Sulfoxides
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Thiocyanates, versatile building blocks in organic synthesis, are shown to be easily accessible via an interrupted Pummerer reaction of sulfoxides. This facile dealkylative functionalization proceeds under mild conditions through electrophilic activation of the sulfoxide partner. The resulting thiocyanate itself can serve as a handle for diversification in a straightforward one-pot procedure.
- Todorovi?, Uro?,Klose, Immo,Maulide, Nuno
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supporting information
p. 2510 - 2513
(2021/04/13)
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- Selectfluor-initiated cyanation of disulfides to thiocyanates
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A Selectfluor-initiated cyanation of disulfides to thiocyanates has been developed. In this process, Selectfluor was employed as the oxidant and trimethylsilyl cyanide was used as the cyanation reagent. It provides an eco-friendly and simple way to synthesize the thiocyanates.
- Zhou, Pengpeng,Chen, Chuan,Li, Shubai
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p. 376 - 380
(2020/02/13)
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- An electrochemical method for deborylative seleno/thiocyanation of arylboronic acids under catalyst- And oxidant-free conditions
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An electrochemical deborylative seleno/thiocyanation of arylboronic acids has been well established to synthesize the corresponding aryl seleno/thiocyanates with good functional group tolerance under ambient conditions. A gram-scale reaction has been performed to highlight the advantages of the protocol. Preliminary mechanistic studies indicate that the oxidation of the seleno/thiocyanate anion occurs prior to that of the arylboronic acid substrate in galvanostatic mode, and that free radicals are involved in the process.
- He, Dongdong,Yao, Jiaojiao,Ma, Boling,Wei, Jinghao,Hao, Guangguo,Tuo, Xun,Guo, Shengmei,Fu, Zhengjiang,Cai, Hu
-
supporting information
p. 1559 - 1564
(2020/03/26)
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- N -Thiocyanato-dibenzenesulfonimide: A new electrophilic thiocyanating reagent with enhanced reactivity
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A novel electrophilic thiocyanating reagent, N-thiocyanato-dibenzenesulfonimide, was prepared and exhibited enhanced electrophilicity with a wide scope of substrates. Thus, it reacted with activated aromatics such as phenols, indoles, anilines and anisoles without a catalyst giving the corresponding thicyanate derivatives in high yields, while TfOH for unactivated arenes and hetero aromatics and Zn(OTf)2 for ketones was used as the catalyst, respectively. It is noteworthy that internal alkenes and styrenes were bifunctionalized giving 1,2-amino thiocyanates in high yields.
- Li, Chengqiu,Long, Pingliang,Wu, Haopeng,Yin, Hongquan,Chen, Fu-Xue
-
supporting information
p. 7131 - 7134
(2019/08/07)
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- Fluorium-Initiated Dealkylative Cyanation of Thioethers to Thiocyanates
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Thioethers are converted to thiocyanates via fluorium-initiated dealkylative cyanation. Selectfluor is used as the oxidant, and trimethylsilyl cyanide is used as the cyanation reagent. The well-streamlined procedure is user-friendly, operationally simple, and step-economical. The current mechanistic studies show that the sulfur radical cation and cyano radical are both involved. They combine to deliver cyanosulfonium, an intermediate toward thiocyanate after dealkylation. Alternatively, a nucleophilic mechanism is also possible. Our dealkyaltive cyanation is also efficient in synthesizing thiocyanates with strongly electrophilic functionalities.
- Chen, Yang,Qi, Hongyi,Chen, Ning,Ren, Demin,Xu, Jiaxi,Yang, Zhanhui
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p. 9044 - 9050
(2019/08/12)
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- Electrochemical ipso-Thiocyanation of Arylboron Compounds
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An operationally simple electrochemical method for the transition-metal-free ipso-thiocyanation of arylboronic acids and aryl trifluoroborates has been developed. The SCN electrophile is generated in situ by anodic oxidation of thiocyanate anions, which avoids formation of salt waste and prevents unwanted side reactions arising from chemical oxidants. The reaction proceeds regiospecifically, and the scope extends to non-activated aromatic systems. (Figure presented.).
- Dyga, Marco,Hayrapetyan, Davit,Rit, Raja K.,Goo?en, Lukas J.
-
supporting information
p. 3548 - 3553
(2019/04/26)
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- Direct Photocatalytic S-H Bond Cyanation with Green cN Source
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Herein we report a novel C-S bond cleavage and reconstruction strategy for the synthesis of thiocyanates through direct photocatalytic S-H bond cyanation from thiols and inorganic thiocyanate salts. In our strategy, the unprecedented example of cutting off C-S bond of SCN- to deliver the green CN sources is demonstrated. This transformation features nontoxic and inexpensive CN sources, available starting materials, metal-/base-/ligand-/peroxide-free, high step economy and mild conditions. It leads to the construction of various thiocyanates and some medicinally and biologically active thiocyanate-containing molecules.
- Guo, Wei,Tan, Wen,Zhao, Mingming,Zheng, Lvyin,Tao, Kailiang,Chen, Deliang,Fan, Xiaolin
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p. 6580 - 6588
(2018/05/29)
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- Preparation method for thiocyanide compound
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The invention discloses a preparation method for a thiocyanide compound. The preparation method comprises the following steps: taking a sulfhydryl compound, thiocyanate as raw materials, taking rose-bengal, eosine Y or eosin B as a catalyst, performing illumination, generating a thiocyanide compound after the illumination reaction. According to the preparation method provided by the invention, thiocyanide is decomposed into thiocyanate ions; the sulfhydryl compound generates sulfhydryl radical under the action of light and the catalyst, and the sulfhydryl radical is used for attacking carbon atoms in thiocyanate ions to obtain a intermediate; sulfide is removed from the intermediate to obtain the thiocyanide compound. The rose-bengal, the eosine Y or the eosin B used by the method containno heavy metal ion, and the adverse effect on the performance of the thiocyanide compound by the heavy metal ion residue is avoided; in addition, the catalyst is easily removed, so that a favorable condition is provided for the preparation of the thiocyanide compound with higher purity.
- -
-
Paragraph 0074; 0075; 0080; 0081
(2018/06/16)
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- Copper-catalyzed cyanothiolation to incorporate a sulfur-substituted quaternary carbon center
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Sulfur-containing nitriles have important research value in the life sciences due to their diverse biological activities resulting from the sulfur and cyano functional groups. Herein, a copper-catalyzed cyanothiolation of N-tosylhydrazones with thiocyanates to generate α-arylthioalkanenitriles bearing sulfur-substituted quaternary carbon center atoms has been described. This novel protocol involves the procedure of copper carbene species promoting S-CN bond cleavage and C-CN/C-S bond reconstruction to introduce both sulfur and cyano groups onto a single carbon center. This cyanothiolation reaction will greatly enhance the synthetic utility of carbenoid species as new entries for the construction of diverse heteroatom-containing nitriles via cyanofunctionalization of metal-carbene species.
- Huang, Yubing,Li, Xianwei,Wang, Xu,Yu, Yue,Zheng, Jia,Wu, Wanqing,Jiang, Huanfeng
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p. 7047 - 7051
(2017/10/05)
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- One-pot synthesis of (ethoxycarbonyl)difluoromethylthioethers from thiocyanate sodium and ethyl 2-(trimethylsilyl)-2,2-difluoroacetate (TMS-CF2CO2Et)
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An efficient one-pot cascade methodology for the synthesis of (ethoxycarbonyl)difluoromethyl thioethers is described. Benzyl, allyl, alkyl halides or diazonium salts as the starting materials together with thiocyanate sodium and TMS-CF2CO2Et in the presence of CsF or NaOAc afford a variety of the fluoroalkylthiolated products in moderate to good yields.
- Xu, Lijun,Wang, Hongyu,Zheng, Changwu,Zhao, Gang
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p. 6057 - 6066
(2017/09/23)
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- Synthesis of perfluoroalkyl thioethers from aromatic thiocyanates by iron-catalysed decarboxylative perfluoroalkylation
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Easily available aryl and heteroaryl thiocyanates were converted into the corresponding perfluoroalkyl thioethers via decarboxylation of potassium perfluoroalkylcarboxylates, catalysed by the inexpensive and environmentally benign iron(III) chloride.
- Exner, Benjamin,Bayarmagnai, Bilguun,Matheis, Christian,Goossen, Lukas J.
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supporting information
p. 89 - 93
(2017/06/23)
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- Molybdenum-doped α-MnO2 as an efficient reusable heterogeneous catalyst for aerobic sulfide oxygenation
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Oxygenation of sulfides to sulfoxides and/or sulfones is an important transformation, and the development of efficient heterogeneous catalysts for oxygenation, which can utilize O2 as the terminal oxidant, is highly desired. In this study, we have successfully developed manganese oxide-based efficient heterogeneous catalysts for aerobic oxygenation of sulfides. Firstly, we prepared four kinds of manganese oxides possessing different crystal structures, such as α-MnO2, β-MnO2, γ-MnO2, and δ-MnO2, and their structure-activity relationships were examined for the aerobic oxygenation of thioanisole. Amongst them, α-MnO2 showed the best catalytic performance for the oxygenation. Moreover, α-MnO2 was highly stable during the catalytic oxygenation possibly due to the tunnel K+ ions. In order to further improve the catalytic performance of α-MnO2, substitutional doping of transition metal cations, such as Mo6+, V5+, Cr3+, and Cu2+, into the framework was carried out. Undoped α-MnO2 possessed a fibrous morphology. When high-valent transition metal cations were doped, especially Mo6+, the lengths of the fibers drastically shortened to form grain-like aggregates of ultrafine nanocrystals, resulting in an increase in specific surface areas and the numbers of catalytically active surface sites. In the presence of Mo6+-doped α-MnO2 (Mo-MnO2), various kinds of sulfides could efficiently be oxidized to the corresponding sulfoxides as the major products. The observed catalysis was truly heterogeneous, and Mo-MnO2 could repeatedly be reused while keeping its high catalytic performance. Besides sulfide oxygenation, Mo-MnO2 could efficiently catalyze several aerobic oxidative functional group transformations through single-electron transfer oxidation processes, namely, oxygenation of alkylarenes, oxidative α-cyanation of trialkylamines, and oxidative S-cyanation of benzenethiols.
- Uematsu, Tsubasa,Miyamoto, Yumi,Ogasawara, Yoshiyuki,Suzuki, Kosuke,Yamaguchi, Kazuya,Mizuno, Noritaka
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p. 222 - 233
(2015/12/31)
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- Transition-metal-free cross-coupling of thioethers with aryl(cyano)iodonium triflates: A facile and efficient method for the one-pot synthesis of thiocyanates
-
A novel transition-metal-free cross-coupling method for the one-step synthesis of thiocyanates via the C-S bond cleavage of readily available thioethers with aryl(cyano)-iodonium triflates as the cyanating agent is developed. This process features relatively broad substrate scopes, less-toxic hypervalent iodine reagents, mild operating conditions, excellent functional group compatibilities, and affords various thiocyanates in moderate to good yields. This journal is
- Zhu, Dan,Chang, Denghu,Shi, Lei
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p. 7180 - 7183
(2015/04/27)
-
- General and practical formation of thiocyanates from thiols
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A new method for the cyanation of thiols and disulfides using cyanobenziodoxol(on)e hypervalent iodine reagents is described. Both aliphatic and aromatic thiocyanates can be accessed in good yields in a few minutes at room temperature starting from a broad range of thiols with high chemioselectivity. The complete conversion of disulfides to thiocyanates was also possible. Preliminary computational studies indicated a low energy concerted transition state for the cyanation of the thiolate anion or radical. The developed thiocyanate synthesis has broad potential for various applications in synthetic chemistry, chemical biology and materials science.
- Frei, Reto,Courant, Thibaut,Wodrich, Matthew D.,Waser, Jerome
-
supporting information
p. 2662 - 2668
(2015/02/05)
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- A mild copper-catalyzed aerobic oxidative thiocyanation of arylboronic acids with TMSNCS
-
A facile and efficient transformation of arylboronic acids to their corresponding aryl thiocyanates has been successfully developed. Based on the CuCl-catalyzed oxidative cross-coupling reaction between arylboronic acids and trimethylsilylisothiocyanate (TMSNCS) under oxygen atmosphere, the transformation can be readily conducted at ambient temperature. The newly-developed protocol provided a competitive synthetic approach to aryl thiocyanates that can tolerate a broad range of reactive functional groups and/or strong electron-withdrawing groups.
- Sun, Nan,Che, Liusheng,Mo, Weimin,Hu, Baoxiang,Shen, Zhenlu,Hu, Xinquan
-
supporting information
p. 691 - 696
(2015/02/19)
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- Practical access to aromatic thiocyanates by CuCN-mediated direct aerobic oxidative cyanation of thiophenols and diaryl disulfides
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The practical and mild aerobic oxidative CuCN-mediated cyanation of thiophenols and diaryl disulfides was investigated. The reaction was performed in air at room temperature and reached aromatic thiocyanates in moderate to good yields starting from a broad range of diversely functionalized substrates.
- Castanheiro, Thomas,Gulea, Mihaela,Donnard, Morgan,Suffert, Jean
-
supporting information
p. 7814 - 7817
(2015/02/19)
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- Copper-catalyzed cyanation of disulfides by azobisisobutyronitrile leading to thiocyanates
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The copper-catalyzed cyanation of disulfides by azobisisobutyronitrile (AIBN) was developed, leading to thiocyanates in moderate to good yields. This procedure tolerates a series of functional groups, such as chloro, nitro, methyl and methoxycarbonyl in the phenyl ring of disulfides. Notably, it enables the use of two ArS units in (ArS)2. CuI was found to be essential for the in situ formation of cyanide anions. This journal is
- Teng, Fan,Yu, Jin-Tao,Yang, Haitao,Jiang, Yan,Cheng, Jiang
-
supporting information
p. 12139 - 12141
(2014/12/11)
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- Synthesis of aryl thiocyanates via copper-catalyzed aerobic oxidative cross-coupling between arylboronic acids and KSCN
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A new protocol for the preparation of aryl thiocyanates by the cross-coupling reaction of arylboronic acids with KSCN salt is described. The coupling reaction was catalyzed by 20 mol% of copper acetate in the presence of 2.0 equivalents 4-methylpyridine serving both as ligand and base under 0.2 MPa of molecular oxygen. A variety of arylboronic acids, including those with substituents at ortho position, were suitable under the reaction conditions. Georg Thieme Verlag Stuttgart · New York.
- Sun, Nan,Zhang, Han,Mo, Weimin,Hu, Baoxiang,Shen, Zhenlu,Hu, Xinquan
-
supporting information
p. 1443 - 1447
(2013/07/26)
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- Efficient and novel method for thiocyanation of aromatic compounds using trichloroisocyanuric acid/ammonium thiocyanate/wet SiO2
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An efficient and novel method for thiocyanation of aromatic and heteroaromatic compounds using trichloroisocyanuric acid/ammonium thiocyanate/wet SiO2 is described. Copyright Taylor & Francis Group, LLC.
- Akhlaghinia, Batool,Pourali, Ali-Reza,Rahmani, Marzieh
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experimental part
p. 1184 - 1191
(2012/04/04)
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- Anodic thiocyanation of mono-and disubstituted aromatic compounds
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The in situ and environmentally friendly thiocyanation (no use of toxic oxidizing agents) electrochemical thiocyanation of aromatic compounds involving various derivatives of anisole and aniline to afford aromatic thiocyanates have been studied in organic
- Gitkis, Anna,Becker, James Y.
-
experimental part
p. 5854 - 5859
(2011/01/07)
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- Synthesis of aryl thiocyanates using Al2O3/MeSO 3H (AMA) as a novel heterogeneous system
-
Indoles and various aromatic and heteroaromatic compounds undergo smooth thiocyanation with ammonium thiocyanate in the presence of a mixture of Al 2O3, MeSO3H (AMA) under mild conditions without use of any organic solvent
- Hosseini-Sarvari, Mona,Tavakolian, Mina
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experimental part
p. 318 - 321
(2009/04/16)
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- Catalytic thiocyanation of aryldiazonium salts in the presence of copper salts
-
Aryldiazonium fluoroborates readily react with potassium thiocyanate in the presence of the CuI/CuII/Phen catalytic system to give arylthiocyanates in high yields.
- Beletskaya, Irina P.,Sigeev, Alexander S.,Peregudov, Alexander S.,Petrovskii, Pavel V.
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p. 250 - 251
(2007/10/03)
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- Highly diastereoselective strecker reaction of enolizable aliphatic sulfinimines
-
The reaction of chiral sulfinimines 1c-g derived from aliphatic aldehydes with TMSCN in the presence of CsF gave α-amino nitriles in high diastereoselectivity and yield. α,β-Diamino acid derivatives were also obtained in high diastereoselectivity from the reaction of 2-aziridinesulfinimines 1h and 1i followed by ring-opening of the products with thiophenol. The presence ofhydrogen of hydrogen at the α-position of the C=N double bond is crucial in this TMSCN addition reaction.
- Li, Bin-Feng,Yuan, Ke,Zhang, Ming-Jie,Wu, Hao,Dai, Li-Xin,Wang, Quan Rui,Hou, Xue-Long
-
p. 6264 - 6267
(2007/10/03)
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- An efficient synthetic route to aryl thiocyanates from arenesulfinates
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An efficient procedure for the conversion ot the inexpensive and readily available arenesulfinate (sodium) salts in three steps into the corresponding aryl thiocyanates is described. Overall yields are high, and the presence of both electron-with drawing and electron-donating substituents is well tolerated.
- Still,Watson
-
p. 1355 - 1359
(2007/10/03)
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- Improved procedure to aryl thiocyanates: A new synthetic application of dry arenediazonium o-benzenedisulfonimides
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Aryl thiocyanates 3 (22 examples) were easily prepared by reaction of dry arenediazonium o-benzenedisulfonimides 1 and sodium thiocyanate (2) in anhydrous acetonitrile at room temperature (20-25 °C) in the presence of copper powder (Procedure A) and at 50 °C or room temperature without the metal catalyst (Procedure B). The yields were from very good to excellent in Procedure A (average yield = 83%), and from modest to excellent in Procedure B (average yield = 63%). In comparison with the thiocyanod-ediazoniation carried out under traditional Sandmeyer-type conditions, the yields of 3 were higher and the isothiocyanate isomers were formed only in traces. Moreover, the results obtained in the absence of copper confirm the role of the anion of salts 1 as an electron transfer agent.
- Barbero,Degani,Diulgheroff,Dughera,Fochi
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p. 585 - 590
(2007/10/03)
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- A new preparative method of thiocanates by the solid state thiosulfonate/cyanide reaction
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The mixing and heating of thiosulfonates with potassium cyanide in the solid state gave a variety of thiocyanates in good yield. This method provides easy access to aryl thiocyanates.
- Fujiki, Kiyoko,Yoshida, Eiji
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p. 3289 - 3294
(2007/10/03)
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- Thiocyanatoarylation of α,β,β-Trifluorostyrene
-
Reactions of α,β,β-trifluorostyrene with arenediazonium tetrafluoroborates and potassium thiocyanate result in addition of the aryl and thiocyanato group across the double bond. Unlike other related reactions, the process requires no catalyst. The reaction is accompanied by formation of aryl thiocyanates and aryl isothiocyanates as by-products.
- Bilaya,Obushak,Ganushchak
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p. 995 - 998
(2007/10/03)
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- Copper(I)-mediated novel thiocyanation of nonactivated aryl iodides
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Various aryl thiocyanates 2 were easily prepared in acceptable yields by heating aryl iodides 1 with cuprate complex K[Cu(SCN)2] in N,N-dimethylformamide (DMF).
- Suzuki, Hitomi,Abe, Hajime
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p. 3413 - 3419
(2007/10/03)
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- ASYMMETRIC SYNTHESIS USING ENANTIOPURE SULFINIMINES: A CONVENIENT SYNTHESIS OF α-AMINO ACIDS
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Diethylaluminum cyanide adds stereoselectively to enantiopure sulfinimines 1 and 2 to give diastereomerically enriched α-amino nitriles 3 and 4 which are hydrolyzed in one step to α-amino acids 5 in >95percent ee and good yields.
- Davis, Franklin A.,Reddy, Rajarathnam E.,Portonovo, Padma S.
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p. 9351 - 9354
(2007/10/02)
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- THIOCYANOARYLATION OF VINYL AND VINYLIDENE CHLORIDES
-
A method was developed for the preparation of chlorine-containing aliphatic-aromatic thicyanates (1-chloro- and 1,1-dichloro-1-thiocyanato-2-arylethanes) by reactions of arenediazonium tetrafluoroborates with vinyl chloride and with vinylidene chloride in presence of potassium (sodium or ammonium) thocyanate.A necessary condition for success in the reaction is the presence of a catalyst: Cu(II) or Fe(II) thicyanate.
- Grishchuk, B. D.,Gorbovoi, P. M.,Kudrik, E. Ya.,Ganushchak, N. I
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p. 2396 - 2401
(2007/10/02)
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- Facile Synthesis of Thiocyanate Using Trimethylsilyl Cyanide
-
Arenethiocyanate can be prepared by reaction of trimethylsilyl cyanide with sodium arenesulphinate or arenesulphonyl chloride.
- Kagabu, Shinzo,Maehara, Masaki,Sawahara, Keisuke,Saito, Katsuhiro
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p. 1485 - 1486
(2007/10/02)
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- NON-AQUEOUS CYANATION OF HALIDES USING LITHIUM CYANIDE
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Efficient conversion of various halides into the corresponding nitriles with lithium cyanide in tetrahydrofuran is described.
- Harusawa, Shinya,Yoneda, Ryuji,Omori, Yukie,Kurihara, Takushi
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p. 4189 - 4190
(2007/10/02)
-
- NEW METHODS AND REAGENTS IN ORGANIC SYNTHESIS. 23. DIETHYL PHOSPHOROCYANIDATE(DEPC): A USEFUL REAGENT FOR AN UNPRECEDENTED TRANSFORMATION OF SULFINIC ACIDS TO THIOCYANATES
-
Diethyl phosphorocyanidate(DEPC) can be efficiently used for a simple, one-step transformation of sulfinic acids to thiocyanates.
- Harusawa, Shinya,Shioiri, Takayuki
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p. 447 - 448
(2007/10/02)
-
- Heterocycles in Organic Synthesis. Part 36. An Alternative to the Gattermann Reaction for the Conversion of Anilines into Thiocyanates
-
5,6-Dihydro-2,4-diphenylnaphthopyrylium thiocyanate is prepared in high yield.It reacts with primary arylamines to yield the corresponding fused pyridinium thiocyanates which when pyrolysed with a KNCS-NaCNS eutectic at ca. 220 deg C give the aryl thiocyanates in yields averaging 80percent.
- Katritzky, Alan R.,Thind, Sukhpal S.
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p. 865 - 868
(2007/10/02)
-