- 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
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p. 4683 - 4689
(2021/09/10)
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- Metal-Free Synthesis of Aryl Selenocyanates and Selenaheterocycles with Elemental Selenium
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This work reports a green method for the synthesis of aryl selenocyanates via a three-component reaction of arylboronic acids, Se powder, and trimethylsilyl cyanide (TMSCN) under metal-free and additive-free conditions. Remarkably, TMSCN acts as not only the substrate, but also the catalyst. Various selenaheterocycles can be also accessed with a catalytic amount of TMSCN.
- Huang, Xiao-Bo,Liu, Miao-Chang,Wu, Hua-Yue,Zhang, Xue,Zhou, Yun-Bing
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supporting information
p. 944 - 948
(2020/12/18)
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- Preparation method of arylselenocyanate compound
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The invention discloses a simple and convenient method for synthesizing arylselenocyanate through reaction of three components, namely arylboronic acid, selenium powder and TMSCN under the conditionsof no metal and no additive. The preparation method has the advantages of no metal participation, no additive promotion, wide substrate range and good functional group compatibility, and provides an efficient and green way for the preparation of various aryl selenocyanates in a highly simple manner.
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Paragraph 0021-0022; 0027-0028; 0057-0059
(2020/12/29)
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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
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supporting information
p. 1559 - 1564
(2020/03/26)
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- Synthesis method of aryl selenocyanate compounds
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The invention relates to the field of synthesis of chemical products, in particular to a synthesis method of aryl selenocyanate compounds. The method starts from arylboronic acid which is easy to obtain, KSeCN which is the cheapest is used as a selenocyanate source, environment-friendly pollution-free current is adopted as a reaction driver, and under conditions of air and a room temperature, arylselenocyanates are efficiently synthesized. Compared with a conventional aryl selenocyanate synthesis method, the method has the obvious advantages that reaction raw materials (including the arylboronic acid) are cheap and easy to obtain, the current causes the lowest pollution to the environment, multiple kinds of functional groups of aromatic rings have good tolerance, yields are high, and thelike. The method can be applied to synthesis of a wide variety of fields of medicines, materials, natural products and the like of the industrial circles and the academic circles.
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Paragraph 0080-0082; 0086
(2020/02/14)
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- Metal-Free ipso -Selenocyanation of Arylboronic Acids Using Malononitrile and Selenium Dioxide
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The first ipso -selenocyanation of arylboronic acids is achieved using selenium dioxide and malononitrile under mild conditions. The reaction is successful even without metal or base in DMSO. The major advantages of this new method are an easy set-up, excellent yields, and the use of odorless and inexpensive selenium reagents. Basic conditions subsequently afford new access to diaryldiselenides in good yields without isolating the organoselenocyanate intermediates.
- Broggi, Julie,Kosso, Anne Roly Obah,Redon, Sébastien,Vanelle, Patrice
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supporting information
p. 3758 - 3764
(2019/09/30)
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- A convenient, transition metal-free synthesis of difluoromethyl selenoethers from organic selenocyanates and TMSCF2H
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An efficient and transition metal-free method for the synthesis of aryl or alkyl difluoromethyl selenides (RSeCF2H) from the corresponding selenocyanates (RSeCN) and TMSCF2H/t-BuOK is described. The reaction performed in THF at 0 °C for 24 h or at room temperature for 6 h supplied a series of RSeCF2H in good to high yields. The successful preparation of difluoromethylselenolated sulfadimethoxine derivative and the scaled-up synthesis of 1-benzyl-5-((difluoromethyl)selanyl)indoline, as examples, suggested good practicability of this method. Advantages of the reaction include mild reaction conditions, good functional group tolerance, a wide range of substrates, and high efficiency. This protocol offered a number of novel difluoromethyl selenoethers, which would accelerate use of such compounds in the areas of life science.
- Dong, Tao,Nie, Jing,Zhang, Cheng-Pan
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p. 5642 - 5649
(2018/08/22)
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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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- Metal-free synthesis of unsymmetrical organoselenides and selenoglycosides
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A one-pot, metal-free procedure has been developed to synthesize unsymmetrical organoselenides. In the first step of the reaction, arylation of potassium selenocyanate (KSeCN) with an iodonium reagent proceeds in the absence of a metal catalyst to produce
- Guan, Yong,Townsend, Steven D.
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supporting information
p. 5252 - 5255
(2017/11/06)
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- Nitromethane as a cyanating reagent for the synthesis of thiocyanates
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Nitromethane has been developed to be an effective cyanating reagent for the synthesis of thiocyanates. In the presence of iodine and base, a wide range of disulfides were reacted with nitromethane smoothly to give diverse thiocyanates in moderate to good yields.
- Wang, Zuo-Hui,Ji, Xiao-Ming,Hu, Mao-Lin,Tang, Ri-Yuan
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supporting information
p. 5067 - 5070
(2015/08/06)
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- 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
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supporting information
p. 2662 - 2668
(2015/02/05)
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- Mechanistic study of the ring-enlargement reaction of (3-oxa-2-silacyclopentyl)methyl radicals into 4-oxa-3-silacyclohexyl radicals. Evidence for a pentavalent silicon-bridging radical transition state in 1,2-rearrangement reactions of β-silyl radicals
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A mechanistic study was performed on a novel radical ring-enlargement reaction of (3-oxa-2-silacyclopentyl)methyl radicals into 4-oxa-3-silacyclohexyl radicals. Two pathways, one via a pentavalent silicon-bridging radical transition state (or intermediate
- Shuto, Satoshi,Sugimoto, Isamu,Abe, Hiroshi,Matsuda, Akira
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p. 1343 - 1351
(2007/10/03)
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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)
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- OXYDATION OF SECONDARY AMINES TO α-CYANOAMINES
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The dehydrogenation of secondary amines with phenylseleninic anhydride or acid under mild conditions in the presence of either sodium cyanide or trimethylsilylcyanide gives good yields of α-cyanoamines.These compounds can be regarded as protected imines, or as a source of α-amino-acids.
- Barton, Derek H. R.,Billion, Annick,Boivin, Jean
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p. 1229 - 1232
(2007/10/02)
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- Se-Phenyl Areneselenosulfonates: Their Facile Formation and Striking Chemistry
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Benzeneseleninic acid reacts rapidly at 0 deg C with aromatic sulfinic acids according to the stoichiometry of eq 3 to form Se-phenyl arenesulfonates, PhSeSO2Ar (2), in high yield.In contrast to thiosulfonates, PhSSO2Ar, areneselenosulfonates are extremely photosensitive and undergo quite rapid photodecomposition.The principal products of this photodecomposition are the sulfonic anhydride, ArSO2OSO2Ar, and diphenyl diselenide.In the presence of added alkenes the facile photodissociation of 2 can be used to initiate a free-radical chain reaction that results in the addition of 2 to the alkene to form β-phenylseleno sulfones in good yield.The β-phenylseleno sulfones can be converted to synthetically useful α,β-unsaturated sulfones by oxidation of the β-phenylseleno group to the corresponding selenoxide and subsequent elimination of PhSeOH.Photoaddition of 2 to 2,5-norbornadiene to 5-(phenylseleno)-exo-3-nortricyclyl aryl sulfone as the almost exclusive product, while photoaddition to 1,5-cyclooctadiene gives a mixture of approximately equal amounts of the 1,2-adduct, 5-(phenylseleno)-6-arenesulfonyl-1-cyclooctene, and the product of transannular addition, 6-(phenylseleno)-exo-2-arenesulfonyl-cis-bicyclooctane.Besides their extraordinary ease of photodissociation, compounds 2 also react extremely readily with nucleophiles: Nu- + PhSeSO2Ar -> PhSeNu + ArSO2-.Kinetic studies show that the reactivity of PhSeSO2Ar with cyanide ion in such a reaction is 70000 times larger than the reactivity of the corresponding thiosulfonate, PhSSO2Ar.
- Gancarz, Roman A.,Kice, John L.
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p. 4899 - 4906
(2007/10/02)
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- A CONVENIENT SYNTHESIS OF PHENYL SELENOCYANATE
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Treatment of benzeneselenenyl chloride with trimethylsilyl cyanide in various organic solvents provided phenyl selenocyanate in virtually quantitative yield.The reaction presents a very simple preparation of the useful selenenylation agent.
- Tomoda, Shuji,Takeuchi, Yoshito,Nomura, Yujiro
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p. 1069 - 1070
(2007/10/02)
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