- Radical Polymerization Behavior of Phenylallene. Synthesis of Functional Polymer Containing Styryl Moiety on the Backbone
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Radical homopolymerization of phenylallene (PA) and copolymerization of PA with some vinyl monomers were described.PA polymerized selectively by the terminal double bond of allene both in the homopolymerization and the copolymeriation.The radical reaction
- Yokozawa, Tsutomu,Ito, Naoro,Endo, Takeshi
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- Selectivity control in thiol-yne click reactions: Via visible light induced associative electron upconversion
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An associative electron upconversion is proposed as a key step determining the selectivity of thiol-yne coupling. The developed synthetic approach provided an efficient tool to access a comprehensive range of products-four types of vinyl sulfides were prepared in high yields and selectivity. We report practically important transition-metal-free regioselective thiol-yne addition and formation of the demanding Markovnikov-type product by a radical photoredox process. The photochemical process was directly monitored by mass-spectrometry in a specially designed ESI-MS device with green laser excitation in the spray chamber. The proposed reaction mechanism is supported by experiments and DFT calculations. This journal is
- Ananikov, Valentine P.,Burykina, Julia V.,Gordeev, Evgeniy G.,K?nig, Burkhard,Shlapakov, Nikita S.
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p. 10061 - 10070
(2020/10/13)
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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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- Alkyne hydrothiolation catalyzed by a dichlorobis(aminophosphine) complex of palladium: Selective formation of cis-configured vinyl thioethers
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Cis all round: Dichlorobis[1-(dicyclohexylphosphanyl)piperidine]palladium, [(P{(NC5H10)(C6H11) 2})2Pd(Cl)2], is a highly efficient alkyne hydrothiolation catalyst and the first generally applicable system that selectively generates cis-configured anti-Markovnikov adducts in excellent yields within only a few minutes at 120 °C in the presence of only 0.05 mol % of the catalyst (see scheme).
- Gerber, Roman,Frech, Christian M.
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scheme or table
p. 8901 - 8905
(2012/09/25)
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- Regio- and stereoselective copper-catalyzed addition of aromatic and aliphatic thiols to terminal and internal nonactivated alkynes
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The CuI-catalyzed regio- and stereoselective hydrothio-lation of terminal and internal alkynes affords (Z) - alkenylsulfides. The following isomerization of the Z-isomers into E-isomers catalyzed by CuI is described. Georg Thieme Verlag Stuttgart · New Yo
- Trostyanskaya, Inna G.,Beletskaya, Irina P.
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experimental part
p. 535 - 540
(2012/04/10)
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- Highly regio- and stereoselective hydrothiolation of acetylenes with thiols catalyzed by a well-defined supported Rh complex
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Highly regio- and stereoselective hydrothiolation of a wide range of alkynes with various thiols was demonstrated in the presence of a well-defined Rh complex supported on mesoporous SBA-15 silica. The catalyst was easily recovered and reused several times without significant loss of activity or selectivity.
- Yang, Yong,Rioux, Robert M.
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supporting information; experimental part
p. 6557 - 6559
(2011/06/28)
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- Gold-catalyzed regiospecific intermolecular hydrothiolation of allenes
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AuBr3-catalyzed regiospecific intermolecular hydrothiolation of aromatic allenes and aromatic thiols afforded the corresponding dithioacetals in good yields at 0°C in 5 min.
- Menggenbateer,Narsireddy, Meda,Ferrara, Giovanni,Nishina, Naoko,Jin, Tienan,Yamamoto, Yoshinori
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scheme or table
p. 4627 - 4629
(2010/09/18)
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- Reductive addition of the benzenethiyl radical to alkynes by amine-mediated single electron transfer reaction to diphenyl disulfide
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Hydrothiolation of alkynes proceeds with diphenyl disulfide and tripropylamine. Amine-mediated single electron transfer to diphenyl disulfide can be proposed for the reaction mechanism. Applications of the method to radical cyclizations of eneyne compound
- Taniguchi, Tsuyoshi,Fujii, Tatsuya,Ldota, Atsushi,Lshibashi, Hiroyuki
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supporting information; experimental part
p. 3298 - 3301
(2009/12/01)
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- Copper-catalyzed synthesis of β-haloalkenyl chalcogenides by addition of dichalcogenides to internal alkynes and its application to synthesis of (Z)-tamoxifen
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A copper-catalyzed synthesis of β-haloalkenyl sulfides or selenides was carried out by addition of dichalcogenides and tetrabutylammonium halides to internal alkynes. The present reaction anti- and regio-selectively afforded the corresponding alkenyl chal
- Taniguchi, Nobukazu
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supporting information; experimental part
p. 2782 - 2790
(2009/08/15)
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- Synthesis of ketene (S, Te) acetals and their transformation into Z-α- phenylthio-α,β-unsaturated aldehydes
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Reaction of thiomethyl phosphonates with aryl (or butyl) tellurenyl halides and aldehydes under basic conditions provides moderate to good yields of ketene thio (telluro) acetals, with vinylic sulfides being byproducts of this transformation. Tellurium-li
- Silveira, Claudio C.,Perin, Gelson,Braga, Antonio L.,Dabdoub, Miguel J.,Jacob, Raquel G.
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p. 7421 - 7432
(2007/10/03)
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- Highly regio- and stereocontrolled synthesis of vinyl sulfides via transition-metal-catalyzed hydrothiolation of alkynes with thiols
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Regio- and stereoselectivity in the hydrothiolation of alkynes with thiols in the presence of a variety of transition-metal catalysts is investigated in detail. Among the catalysts employed, RhCl(PPh3)3 exhibits excellent catalytic ability toward the anti-Markovnikov addition of thiols (ArSH) to alkynes (RC≡CH), which affords the corresponding vinylic sulfides (trans-RCH=CHSAr) regio- and stereoselectively. The reaction may proceed by the formation of hydrorhodium sulfide species (H-[Rh]-SAr) and probably via the subsequent hydrorhodation of alkynes to provide vinylrhodium intermediates (RCH=CH-[Rh]-SAr). In contrast, PdCl2(PhCN)2-catalyzed hydrothiolation of aromatic alkynes (ArC≡CH) takes place to give the corresponding Markovnikov adducts (R(ArS)C=CH2) with excellent regioselectivity, probably via thiopalladation of alkynes by palladium sulfide species (ArS-[Pd]-Cl), which may be formed by ligand-exchange reaction between PdCl2(PhCN)2 and ArSH. Furthermore, in the case of alkynes bearing propargylic protons (R'CH2C≡CH), a sequential addition/isomerization reaction occurs to provide the internal vinylic sulfides (R'CH=C(SAr)CH3) regioselectively. From the same starting materials (alkyne and thiol), therefore, the regioselectivity of hydrothiolation can be attained simply by changing the catalysts, i.e., RhCl(PPh3)3 and PdCl2(PhCN)2.
- Ogawa, Akiya,Ikeda, Takuma,Kimura, Kouichi,Hirao, Toshikazu
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p. 5108 - 5114
(2007/10/03)
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- 182. A Convenient Synthesis of Vinyl Sulfides
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tert-Alkyl sulfides, with an α-(1H-benzotriazol-1-yl) group 6 and 13, are readily prepared from N--1H-benzotriazoles 3 and N-(11), respectively, by reaction with BuLi and then with the appropriate electrophile.The tert-alkyl sulfides 6 a
- Katritzky, Alan R.,Afridi, Amir S.,Kuzmierkiewicz, Wojciech
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p. 1931 - 1935
(2007/10/02)
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- Free-Radical Reactions of Benzenethiol and Diphenyl Disulphide with Alkynes. Chemical Reactivity of Intermediate 2-(Phenylthio)vinyl Radicals
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Reaction of benzenethiol at 100 deg C with neat alkyl- and dialkyl-acetylenes leads to virtually quantitative formation of isomeric mixtures of (E)- and (Z)-vinyl sulphide adducts in ratios which depend largely upon both the extent and the nature of alkyl substitution.Results are explained in terms of rapidly interconverting sp2-hybridized (E)- and (Z)-1-alkyl-2-(phenylthio)vinyl radical intermediates which can undergo hydrogen transfer from benzenethiol to an extent which is essentially dependent upon the steric hindrance of their cis-2-substituent.Consistent results are provided by related radical reactions of diphenyl disulphide with alkyl-substituted alkynes to afford varying amounts of 1,2-bis(phenylthio)ethylene adducts ascribable to SH2 reaction of the resulting 1-alkyl-2-(phenylthio)vinyl radicals with the disulphide present.Under analogous conditions benzenethiol and diphenyl disulphide react with phenylacetylenes to give vinyl sulphide or bissulphide adducts in a trans-stereoselective fashio.The findings are interpreted by suggesting, for the intermediate sp-hybridized 1-phenyl-2-(phenylthio)vinyl radicals, the occurrence of significant bonding interaction between the unpaired electron and the adjacent sulphur, which would essentially prevent attack of radical scavenger on the side cis to PhS.Evidence is also presented that 1-phenyl-2-(phenylthio)vinyl radicals can exhibit homolytic intramolecular cyclization reactions, leading to benzothiophene products to a comparatively much greater extent than the 1-alkyl-2-substituted analogues; however, 1-tert-butyl-2-(phenylthio)vinyl radical would represent a special case.
- Benati, Luisa,Montevecchi, Pier Carlo,Spagnolo, Piero
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p. 2103 - 2109
(2007/10/02)
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- Experimental and Theoretical Study of the Radical-Chain Addition of Benzenethiol to Heterosubstituted Allenes
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The radical-chain addition of benzenethiol to phenylallene (PHA), methoxyallene (MEOA), carbomethoxyallene (CBA), cyanoallene (CNA), chloroallene (ClA), and (phenylthio)- and allene (PHSA and MPHSA) has been studied.In all cases, exc
- Pasto, Daniel J.,L'Hermine, Gael
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p. 685 - 694
(2007/10/02)
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- Facile Reduction of Dithiocarbonates Derived from Secondary Alcohols with n-Bu3SnH-Et3B and Synthesis of 2-Furanthiones and 2-Furanones by Intramolecular Addition of Alkoxythiocarbonyl Free Radicals to Acetylenic Linkages
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The reduction of dithiocarbonates or thiocarbonates by n-Bu3SnH-Et3B easily gives the corresponding hydrocarbons.The intermediate alkoxythiocarbonyl radical equivalents are trapped by properly located carbon-carbon multiple bonds.The dithiocarbonates derived from either homopropargylic or homoallylic alcohols produce tetrahydrofuranones upon treatment with n-Bu3SnH-Et3B.Application of this new method to the conversion of carbonyl compounds into olefins is also described.
- Nozaki, Kyoko,Oshima, Koichiro,Utimoto, Kiitiro
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p. 2578 - 2583
(2007/10/02)
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- A Direct Formation of Alkenyl Chalcogenides from Nonactivated Alkenyl Halides and Diorganyl Dichalcogenides under Neutral Conditions
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Alkenyl sulfides and selenides were easily obtained in moderate to good yields by heating the corresponding bromides with diorganyl disulfides or diselenides in hexamethylphosphoric triamide with or without copper(I) iodide as a promoter.
- Ogawa, Takuji,Hayami, Kazuo,Suzuki, Hitomi
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p. 769 - 772
(2007/10/02)
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- FACILE REDUCTION OF DITHIOCARBONATES WITH n-Bu3SnH-Et3B. EASY ACCESS TO HYDROCARBONS FROM SECONDARY ALCOHOLS
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The reduction of dithiocarbonates or thiocarbonates by n-Bu3SnH-Et3B easily gives the corresponding hydrocarbons.Application of a new method in the conversion of carbonyl compounds into olefins is also described.
- Nozaki, Kyoko,Oshima, Koichiro,Utimoto, Kiitiro
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p. 6125 - 6126
(2007/10/02)
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- A New Syntethic Route to Vinyl Sulfides Utilizing the Reaction of (Phenylthio)carbenes with Nitrile Anions
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Reactions of nitrile anion (LiCR2R3CN) and (phenylthio)carbenes generated from 1-chloroalkyl phenyl sulfides (R1CH(Cl)SPh) 2a-e by the action of n-BuLi have been shown to be a useful synthetic route to vinyl sulfides (PhSC(R1)=CR2R3) 3a-k (34-91percent).The nucleophilic attack of the nitrile anion on the carbenic species gave the presumed intermediate β-(phenylthio)-β-lithionitrile, which eliminated LiCN to give the expected vinyl sulfides.The application of the present reaction to the synthesis of cyclic vinyl sulfides was successful: the decomposition of the dianion ofω,ω-bis(phenylthio)alkanenitriles (8b, 8c, 11, and 14) affording the corresponding 1-(phenylthio)cycloalkenes (9, 10, 12, and 15) in 12-87percent yields.
- Harada, Toshiro,Karasawa, Akio,Oku, Akira
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p. 842 - 846
(2007/10/02)
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- BENZYNE-INDUCED FRAGMENTATION OF 1,3-OXATHIOLANES. A NOVEL METHOD FOR DEPROTECTION OF CARBONYL GROUPS, PREPARATION OF PHENYL VINYL SULFIDES, AND 1,2-CARBONYL TRANSPOSITION
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A variety of 1,3-oxathiolanes undergo a benzyne-induced fragmentation leading to phenyl vinyl sulfides and carbonyl compounds.The reaction developed here provides a novel method for deprotection of carbonyl compounds from 1,3-oxathiolanes, preparation of phenyl vinyl sulfides, and 1,2-carbonyl transposition.
- Nakayama, Juzo,Sugiura, Hidetoshi,Shiotsuki, Atsuko,Hoshino, Masamatsu
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p. 2195 - 2198
(2007/10/02)
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- CROSS-COUPLING REACTION BETWEEN ENOL PHOSPHATES AND ORGANOALUMINIUM COMPOUNDS IN THE PRESENCE OF PALLADIUM(0) CATALYST.
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The title reaction in the presence of a catalytic amount of tetrakis(triphenylphosphine)palladium(0) affords alkylative coupling products in good to excellent yields in 1,2-dichloroethane at room temperature. This coupling reaction under C(sp**2)-O cleavage proceeds stereospecifically. The reaction does not affect a coexisting vinyl sulfide group. This feature enables 1,2- and 1,3-carbonyl transposition with or without alkylation via phenylthio-substituted enol phosphates.
- Takai,Sato,Oshima,Nozaki
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p. 108 - 115
(2007/10/02)
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- Pd(O) PROMOTED ALKYLATION OF ENOL PHOSPHATES WITH ORGANOALUMINIUM COMPOUNDS AND ITS SYNTHETIC APPLICATIONS
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Keto carbonyl 1,2- and 1,3-transpositions with and without alkylation of the substrate are described together with ketone synthesis from thiocarboxylic S-ester.
- Sato, Mitsuyoshi,Takai, Kazuhiko,Oshima, Koichiro,Nozaki, Hitosi
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p. 1609 - 1612
(2007/10/02)
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