- Catalyst and Additive-Free Selective Ring-Opening Selenocyanation of Heterocycles with Elemental Selenium and TMSCN
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A catalyst and additive-free strategy for selective ring-opening selenocyanation of saturated heterocycles with elemental selenium and TMSCN is developed, affording a series of aliphatic selenocyanates and selenaheterocycles. In the case of unprotected unstrained N-heterocycles, the reactions offer ammonium selenonitriles that prove to be an efficient selenonitrile reagent. (Figure presented.).
- Lu, Li-Guo,Bi, Kang,Huang, Xiao-Bo,Liu, Miao-Chang,Zhou, Yun-Bing,Wu, Hua-Yue
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Read Online
- Solvent free nucleophilic selenocyanation with [bmim][SeCN]. Direct access to perfluoroalkylselenide compounds
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Available online-1-n-butyl-3-methylimidazolium selenocyanate ([bmim][SeCN]) proved to be a very efficient reagent for selenocyanation of alkyl halides. As part of an eco-friendly process, no organic solvents were used during the transformation and reaction times are reduced by using microwave as a heating source. The ionic liquid was carefully recycled in two different ways. Selenocyanate compounds were successfully transformed into trifluoromethylselenides in a one-pot two step procedure.
- De-Zordo Banliat, Arnaud,Grollier, Kévin,Damond, Aurélie,Billard, Thierry,Dagousset, Guillaume,Magnier, Emmanuel,Pégot, Bruce
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- AIBN-initiated direct thiocyanation of benzylic sp3C-H with: N -thiocyanatosaccharin
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Direct thiocyanations of benzylic compounds have been implemented. Here, a new strategy, involving a free radical reaction pathway initiated by AIBN, was used to construct the benzylic sp3 C-SCN bond. In this way, the disadvantage of other strategies involving introducing leaving groups in advance to synthesize benzyl thiocyanate compounds was overcome. The currently developed protocol also involved the use of readily available raw materials and resulted in high product yields (up to 100%), both being great advantages for synthesizing benzyl thiocyanates.
- Wu, Di,Duan, Yongjie,Liang, Kun,Yin, Hongquan,Chen, Fu-Xue
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supporting information
p. 9938 - 9941
(2021/10/12)
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- Novel selenocyano reagent as well as preparation method and application thereof
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The invention discloses a novel selenocyano reagent, which has a structure as shown in a formula I. The selenocyano reagent is low in preparation cost, stable in property and easy to store, can be widely applied to selenocyanation reaction of various halogenated hydrocarbon compounds, is applied to preparation of selenocyanate, is mild and simple in reaction condition and easy to implement, and has relatively high selenocyanation efficiency.
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Paragraph 0075-0077
(2021/03/13)
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- (1-Selenocyanatoethyl)benzene: A Selenocyanation Reagent for Site-Selective Selenocyanation of Inert Alkyl C(sp3)-H Bonds
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A new, simple, yet easily accessible, (1-selenocyanatoethyl)benzene has been designed and applied as a SeCN group transfer reagent for selenocyanation of aliphatic C(sp3)-H bonds for the first time. This protocol is featured with mild reaction conditions and wide substrate scope. Control experiments reveal that a radical-group transfer mechanism might be involved.
- Yu, Fei,Li, Chuang,Wang, Chuangye,Zhang, Hongwei,Cao, Zhong-Yan
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supporting information
p. 7156 - 7160
(2021/09/18)
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- Pronounced activity of aromatic selenocyanates against multidrug resistant ESKAPE bacteria
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Selenocyanates represent an interesting class of organic selenium compounds. Due to their similarity with better known natural (iso-)thiocyanates, they promise high biological activity and may also be metabolized to other Reactive Selenium Species (RSeS),
- Nasim, Muhammad Jawad,Witek, Karolina,Kincses, Annamária,Abdin, Ahmad Yaman,?es?awska, Ewa,Mar?, Ma?gorzata Anna,Gajdács, Márió,Spengler, Gabriella,Nitek, Wojciech,Latacz, Gniewomir,Karczewska, El?bieta,Kie?-Kononowicz, Katarzyna,Handzlik, Jadwiga,Jacob, Claus
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supporting information
p. 6021 - 6031
(2019/04/16)
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- Potent anti-proliferative activities of organochalcogenocyanates towards breast cancer
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The pharmacological importance, particularly the anti-cancer and chemopreventive potentials, of organochalcogen compounds has attracted wide research attention recently. Herein we describe the synthesis of a series of organochalcogenocyanates that have one or more selenocyanate or thiocyanate units in a single molecule. The anti-proliferative activity of these organochalcogenocyanates in different breast cancer cells shows that selenocyanates exhibit much higher anti-proliferative activities than thiocyanates in general. Our study reveals that the activity of benzyl selenocyanate (1, BSC) could be significantly enhanced by 4-nitro substitution (12), which was more selective towards triple-negative breast cancer cells (MDA-MB-231) over other ER+ breast cancer cells (MCF-7 and T-47D). Furthermore, to the best of our knowledge, this is the first report on the synthesis of compounds having more than two selenocyanate units with promising anti-proliferative activities. Our studies further indicate that the apoptotic activities of selenocyanates are associated with modulation of cellular morphology and cell cycle arrest at S-phase. Selenocyanates also inhibited cellular migration and exhibited weak antioxidant activities. An effective binding interaction of compound 12 with serum albumin indicates its feasible transport in the bloodstream for its enhanced anti-cancer properties. Mechanistic studies by western blot analysis demonstrate that benzylic selenocyanates exhibit anti-proliferative activities by modulating key cellular proteins such as Survivin, Bcl-2 and COX-2; this was further supported by molecular docking studies. The results of this study would be helpful in designing suitable chemotherapeutic and chemopreventive drugs in the future.
- Banerjee, Kaustav,Padmavathi, Ganesan,Bhattacherjee, Debojit,Saha, Suchismita,Kunnumakkara, Ajaikumar B.,Bhabak, Krishna P.
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p. 8769 - 8782
(2018/11/30)
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- Nucleophilic displacement reactions of 5′-derivatised nucleosides in a vibration ball mill
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Vibration ball-milling in a zirconia-lined vessel afforded clean and quantitative nucleophilic displacement reactions between 4-methoxybenzylthiolate salts and nucleoside 5′-halides or 5′-tosylates in five to 60 minutes. Under these conditions, commonly-e
- Eguaogie, Olga,Conlon, Patrick F.,Ravalico, Francesco,Sweet, Jamie S. T.,Elder, Thomas B.,Conway, Louis P.,Lennon, Marc E.,Hodgson, David R. W.,Vyle, Joseph S.
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supporting information
p. 87 - 92
(2017/02/15)
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- Benzyltrifluoromethyl (or Fluoroalkyl) Selenide: Reagent for Electrophilic Trifluoromethyl (or Fluoroalkyl) Selenolation
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Trifluoromethylseleno substituent (CF3Se) is an emerging group, but its direct introduction onto organic molecules is still quite limited and mainly restricted to nucleophilic methods. Herein, we describe a new approach to easily and safely perform electrophilic trifluoromethylselenolation starting from a simple and easily accessible reagent, namely, benzyltrifluoromethyl selenide. This strategy can be generalized to various fluoroalkylselanyl groups, even functionalized ones.
- Glenadel, Quentin,Ismalaj, Ermal,Billard, Thierry
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p. 8268 - 8275
(2016/09/28)
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- Stereoselective synthesis of alkyl styryl selenides in one-pot: A straightforward approach by in situ dialkyl diselenide formation under transition metal-free conditions
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A simple procedure for the synthesis of alkyl styryl selenides was developed. This methodology involves the in situ generation of selenolate anions by a one-pot and three-step protocol where a nucleophilic substitution between KSeCN and alkyl halides affords the corresponding alkyl selenocyanate in the first step, giving dialkyl diselenide by a further K3PO4-assisted reaction. Subsequent reduction yields the alkyl selenolate anions which react with substituted (E,Z)-β-styryl halides to afford the corresponding vinyl selenides with retention of stereochemistry and from moderate to excellent yields. This procedure does not require a catalyst, proceeds under an air atmosphere and within a short reaction time, and is free from diselenide and malodorous and air-sensitive alkyl selenols as starting materials.
- Heredia, Adrián A.,Pe?é?ory, Alicia B.
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p. 105699 - 105706
(2015/12/26)
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- Tetrazole regioisomers in the development of nitro group-containing antitubercular agents
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Tetrazole derivatives containing nitro substituents have been identified as promising antitubercular agents. In this study, the antitubercular potency, selectivity and toxicity of tetrazole 1,5- and 2,5-regioisomers were examined. We prepared a series of 1- and 2-alkyl-5-benzylsulfanyl-2H-tetrazoles and their selenium analogs with various nitro group substitutions. These 1,5- and 2,5-regioisomers were isolated and unambiguously identified using 1H and/or 13C NMR. Among the prepared compounds, 1- and 2-alkyl-5-[(3,5-dinitrobenzyl)sulfanyl]-2H-tetrazole derivatives and their selenium bioisosteres showed the highest antimycobacterial activity, with minimal inhibitory concentration (MIC) values of approximately 1 μM (0.37-0.46 μg mL-1) against Mycobacterium tuberculosis CNCTC My 331/88. The 2-alkyl regioisomers exhibited consistently higher antimycobacterial activity and lower in vitro toxicity against a mammalian cell line compared to the 1-alkyl isomers. The antimycobacterial activity of the 2-alkyl regioisomers was less influenced by the type of alkyl substituent in contrast to 1-alkyl isomers. Furthermore, the 3,5-dinitrobenzyl moiety per se is not the carrier of mutagenicity. These findings encourage further optimization of the 2-alkyl chain to improve the pharmacokinetic properties and toxicity of 2-alkyl-5-[(3,5-dinitrobenzyl)sulfanyl]-2H-tetrazole lead compounds. This journal is
- Karabanovich, Galina,Roh, Jaroslav,Soukup, Ondej,Pvkov, Ivona,Pasdiorov, Markta,Tambor, Vojtch,Stolakov, Jiina,Vejsov, Marcela,Vvrov, Kateina,Klimeov, Vra,Hrablek, Alexandr
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supporting information
p. 174 - 181
(2015/02/02)
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- Selenocyanates and diselenides: A new class of potent antileishmanial agents
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Thirty five selenocyanate and diselenide compounds were subjected to in vitro screening against Leishmania infantum promastigotes and the most active ones were also tested in an axenic amastigote model. In order to establish the selectivity indexes (SI) t
- Plano, Daniel,Baquedano, Ylenia,Moreno-Mateos, David,Font, María,Jiménez-Ruiz, Antonio,Palop, Juan Antonio,Sanmartín, Carmen
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experimental part
p. 3315 - 3323
(2011/08/03)
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- Experimental and theoretical studies on the nature of weak nonbonded interactions between divalent selenium and halogen atoms
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(Chemical Equation Presented). To investigate the nature of weak nonbonded selenium...halogen interactions (Se...X interactions; X = F, Cl, and Br), three types of model compounds [2-(CH2X)C6H 4SeY (1-3), 3-(CH2
- Iwaoka, Michio,Katsuda, Takayuki,Komatsu, Hiroto,Tomoda, Shuji
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p. 321 - 327
(2007/10/03)
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- Highly chemoselective synthesis of functionalized diselenides from alkyl halides using benzyltriethylammonium tetrathiomolybdate
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A variety of functionalized selenocyanates generated in situ from the corresponding alkyl halides undergo a facile reductive coupling on treatment with benzyltriethylammonium tetrathiomolybdate 1 under very mild conditions to give the corresponding disele
- Prabhu, Kandikere R.,Chandrasekaran, Srinivasan
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p. 1021 - 1022
(2007/10/03)
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- On the Racemization of α-Hetero-Substituted Benzyllithium Compounds
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Benzyllithium compounds carrying a benzylthio substituent (6), a benzylseleno substituent (8), and an isopropyl(methyl)amino substituent 14 have been generated.Racemization barriers have been determined in THF by monitoring the coalescence of signals of d
- Ahlbrecht, Hubertus,Harbach, Juergen,Hoffmann, Reinhard W.,Ruhland, Thomas
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p. 211 - 216
(2007/10/02)
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- ELECTROCHEMICAL SYNTHESIS OF SELENO AND TELLURO DERIVATIVES IN MeCN
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Large-scale electrolysis with concurrent sonication in MeCN allows for the synthesis of a large variety of seleno and telluro derivatives.Aliphatic chalcogenides REER or RER (E = Se, Te) can be prepared by reduction of E powder to E2(2-) or E(2-), followed by addition of an alkyl halide RX.Depending upon R, substitution can compete with homogeneous electron or H+ transfers.RE+ can be prepared by anodic oxidation of REER, and trapped by nucleophiles and olefins.The synthesis of aromatic chalcogenides ArEAr'can be carried out by electrochemically inducedSRN1 substitution.The yields are improved by redox catalysis.Under such conditions, the synthesis of PhEAr (Ar = NCC6H4, PhCOC6H4) proceeds in good yields.ArEEAr and ArEAr can be prepared by cathodic reduction of PhEAr.
- Degrand, Chantal,Prest, Rita,Nour, Mohamed
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p. 201 - 210
(2007/10/02)
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- SYNTHESIS OF SELENOACETALS
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This paper reports our results concerning the syntheses of various bis(alkylseleno)alkanes and some of their arylseleno analogues by different methods.The scope and limitation of each of them are presented.
- Clarembeau, M.,Cravador, A.,Dumont, W.,Hevesi, L,Krief, A.,et al.
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p. 4793 - 4812
(2007/10/02)
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- Selenocyanation using a combined reagent of triphenylphosphine and selenocyanogen. A new and simple synthesis of alkyl selenocyanates and symmetrical alkyl diselenides from alcohols
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A novel reagent Ph3SeCN)2, easily prepared by adding an equimolar amount of tri-phenylphosphine to selenocyanogen solution in methylene chloride and tetrahydrofuran reacts below -60° with primary alcohols to produce directly the corr
- Tamura,Adachi,Kawasaki,Kita
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p. 2251 - 2252
(2007/10/12)
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