- Catalytic conversion of alkynes to α-vinyl sulfides mediated by carbene-linker-carbene (CXC) rhodium and iridium complexes
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The catalytic activity of a set of mono- and bimetallic Rh(i) and Ir(i) complexes bearing carbene-linker-carbene (CXC) bis-triazolylidene ligands (with X = O, N) coordinated in a bridging or chelating fashion was evaluated in the hydrothiolation of alkyne
- Tolley, Lewis C.,Fernández, Israel,Bezuidenhout, Daniela I.,Guisado-Barrios, Gregorio
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p. 516 - 523
(2021/02/09)
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- Safe and Metal-Free Synthesis of 1-Alkenyl Aryl Sulfides and Their Sulfones from Thiiranes and Diaryliodonium Salts
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A series of 1-alkenyl aryl sulfides was synthesized from thiiranes and diaryliodonium salts in tetrahydrofuran in the presence of potassium tert -butoxide. The proposed reaction mechanism involves generation of benzynes from the diaryliodonium salts in the presence of the base. Then, nucleophilic attack of the benzynes by thiiranes, followed by hydrogen abstraction and ring opening of the generated thiiranium intermediates, provides the sulfides. These sulfides were further oxidized with performic acid to the corresponding sulfones. The current method provides a metal-free and safe method for the preparation of 1-alkenyl aryl sulfides and their sulfones.
- Dong, Jun,Xu, Jiaxi
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p. 2407 - 2415
(2018/04/16)
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- A Hemilabile and Cooperative N-Donor-Functionalized 1,2,3-Triazol-5-Ylidene Ligand for Alkyne Hydrothiolation Reactions
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A series of novel cationic and neutral Rh complexes with an N-donor-functionalized 1,2,3-triazol-5-ylidene (TRZ) ligand (in which the pendant N donor is NHBoc, NH2, or NMe2) is described. The catalytic activity of these complexes was
- Strydom, Ian,Guisado-Barrios, Gregorio,Fernández, Israel,Liles, David C.,Peris, Eduardo,Bezuidenhout, Daniela I.
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supporting information
p. 1393 - 1401
(2017/02/05)
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- A rhodium(i)-oxygen adduct as a selective catalyst for one-pot sequential alkyne dimerization-hydrothiolation tandem reactions
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An air-stable rhodium(i)-oxygen adduct featuring a CNC-pincer ligand, based on 1,2,3-triazol-5-ylidenes, catalyzes the homo-dimerization and hydrothiolation of alkynes, affording the gem-enyne and α-vinyl sulfide isomers, respectively, with excellent selectivity. A one-pot stepwise strategy allows the selective catalytic preparation of non-symmetric bis-vinyl sulfides, as well as the alkyne dimerization-hydrothiolation tandem reactions.
- Kleinhans, George,Guisado-Barrios, Gregorio,Liles, David C.,Bertrand, Guy,Bezuidenhout, Daniela I.
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supporting information
p. 3504 - 3507
(2016/03/04)
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- Hydroxo-rhodium-N-heterocyclic carbene complexes as efficient catalyst precursors for alkyne hydrothiolation
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The new Rh-hydroxo dinuclear complexes stabilized by an N-heterocyclic carbene (NHC) ligand of type [Rh(μ-OH)(NHC)(η2-olefin)] 2 (coe, IPr (3), IMes (4); ethylene, IPr (5)) are efficient catalyst precursors for alkyne hydrothiolation
- Palacios, Laura,Artigas, Maria Jose,Polo, Victor,Lahoz, Fernando J.,Castarlenas, Ricardo,Perez-Torrente, Jesus J.,Oro, Luis A.
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p. 2910 - 2919
(2014/01/06)
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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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- Ligand-controlled regioselectivity in the hydrothiolation of alkynes by rhodium N-heterocyclic carbene catalysts
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Rh-N-heterocyclic carbene compounds [Rh(μ-Cl)(IPr)(ν2- olefin)]2 and RhCl(IPr)(py)(ν2-olefin) (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-carbene, py = pyridine, olefin = cyclooctene or ethylene) are highly active cata
- Di Giuseppe, Andrea,Castarlenas, Ricardo,Perez-Torrente, Jesus J.,Crucianelli, Marcello,Polo, Victor,Sancho, Rodrigo,Lahoz, Fernando J.,Oro, Luis A.
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scheme or table
p. 8171 - 8183
(2012/07/13)
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- Water-promoted regioselective hydrothiolation of alkynes
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Water promotes hydrothiolation of unactivated alkynes efficiently without any catalyst or additive. The reaction at room temperature furnishes vinyl sulfides with high regioselectivity via anti-Markovnikov addition. The terminal al- kynes provide dithiola
- Bhadra, Sukalyan,Ranu, Brindaban C.
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experimental part
p. 1605 - 1609
(2010/04/03)
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- Hydroalumination of thioacetylenes: A versatile generation and reactions of α-aluminate sulfides intermediates
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Hydroalumination of thioacetylenes using DIBAL-H and lithium di-(isobutyl)-n-(butyl)-aluminate hydride (Zweifel's reagent), followed by addition of water, furnished exclusively the (Z)- and (E)-vinyl sulfides, respectively. The regio- and stereochemistry
- Guerrero Jr.,Dabdoub,Marques,Wosch,Baroni,Ferreira
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experimental part
p. 4379 - 4394
(2009/04/11)
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- Stereoselective synthesis of (Z)-α-arylsulfenylvinyl tellurides via hydrozirconation of alkynyltellurides
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Hydrozirconation of alkynyltellurides 1 in THF at room temperature gave (Z)-α- tellurenylvinylzirconium complexes 2, which were reacted with arylsulfenyl chlorides 3 to afford stereoselectively (Z)-α- arylsulfenylvinyl tellurides 4 in good yields.
- Cai, Mingzhong,Chen, Junmin
-
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- A facile stereoselective synthesis of (E)-1-arylseleno-2- arylsulfanylethenes via hydrozirconation of arylselenoethynes
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Hydrozirconation of arylselenoethynes 1 gave (E)-2- arylselenovinylzirconium(IV) complexes 2, which reacted with arylsulfenyl chlorides 3 stereoselectively to afford (E)-1-arylseleno-2-arylsulfanylethenes 4 in good yields. (E)-1-Arylseleno-2-arylsulfanyle
- Cai, Ming-Zhong,Jiang, Min-Hua,Li, Hai-Gen
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p. 702 - 704
(2007/10/03)
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- Hydroalumination of phenylthioacetylenes. Synthesis and reactions of (Z)- and (E)-1-butyltelluro-1-phenylthio-1-alkenes
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Hydroalumination of phenylthioacetylenes with the Zweifel's reagent as reducing agent followed by the addition of C4H9TeBr afforded (Z)-telluro(thio)ketene acetals (Z >80-93%). The (E)-isomers were obtained with 100% stereoselectivit
- Dabdoub, Miguel J.,Guerrero Jr., Palimécio G.
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p. 7167 - 7172
(2007/10/03)
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- Hydrochalcogenation of phenylthioacetylenes. Synthesis of mixed (Z)-trisubstituted 1,2-bis(organylchalcogeno)-1-alkenes
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The treatment of 1-phenylthioacetylenes with phenylselenolate and butyl or phenyltellurolate anions generated by the reaction of the corresponding dichalcogenide with NaBH4 in aqueous ethanol results in the formation of mixed 1,2-bis(organylcha
- Dabdoub, Miguel J.,Dabdoub, Vania B.,Pereira, Marco A.
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p. 1595 - 1597
(2007/10/03)
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- Regio- and stereospecific cleavage of α,β-epoxysilanes with lithium phenylsulfide
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Trimethyl- or dimethylphenylsilylepoxides react with lithium phenylsulfide to give regio- and stereodefined vinyl sulfides resulting from α-ring opening and Peterson elimination. When the epoxide bears the bulky tert-butyldiphenylsilyl group the reaction
- Cuadrado, Purificación,González-Nogal, Ana M.
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p. 1111 - 1114
(2007/10/03)
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- Stereoselective synthesis of (E)-vinylsulfides via the reaction of vinylzirconium compounds with disulfides
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Hydrozirconation of alk-1-ynes gives vinyl zirconium complexes, which react with disulfides to afford (E)-vinylic sulfides in high yield.
- Huang, Xian,Xu, Xin-Hua,Zheng, Wei-Xin
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p. 2399 - 2404
(2007/10/03)
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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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- Reactions of Alkylmercurials with Heteroatom-Centered Acceptor Radicals
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The relative reactivities of alkylmercury halides toward PhS., PhSe., or I. decrease drastically from R = tert-butyl to R = sec-alkyl to R = n-butyl, indicative that R. is formed in the rate-determining step in the attack of these radicals upon RHgCl.The alkyl radicals thus formed will enter into chain reactions in which a heteroatom-centered radical (A.) is regenerated from substrates such as RS-SR, ArSe-SeAr, ArTe-TeAr, PhSe-SO2Ar, Cl-SO2Ph; ZCH=CHA (A = Cl, I, SPh, SO2Ph); or PhCCHA (A = I, SPh, SO2Ph). β-Styrenyl (PhCH=CHA, Ph2C=CHA) and β-phenethynyl (PhCCA) systems with A = I, Br, SO2Ph also enter into chain reactions with mercury(II) salts with the ligands PhS, PhSe, PhSO2, or (EtO)2PO.The relative reactivities of a series of reagents toward t-Bu. and of PhCH=CHA, Ph2C=CHA, and PhCCA toward c-C6H11. are reported as well as the regioselectivity of t-Bu. attack observed for 1,2-disubstituted ethylenes (ZCH=CHA) with Z and A from the group Ph, Cl, Br, I, SO2Ph, SPh, Bu3Sn.Reactions of (E)- and (Z)-PhCH=CHI or MeO2CCH=CHI with t-Bu. or c-C6H11. occurred in a regioselective and stereospecific (retention) manner.Reactions of (E)- and (Z)-ClCH=CHCl occurred in a nonstereospecific manner in which the E/Z product ratio increased with the bulk of the attacking radical.A similar effect on the E/Z product ratios was observed for (Z)-MeO2CCH=CHCl.
- Russell, Glen A.,Ngoviwatchai, Preecha,Tashtoush, Hasan I.,Pla-Dalmau, Anna,Khanna, Rajive K.
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p. 3530 - 3538
(2007/10/02)
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- A Stereospecific Route to Olefins through Sequential Coupling Reactions of Grignard Reagents with 1-Bromo-2-phenylthioethene in the Presence of Nickel or Palladium Catalysts
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The room temperature sequential formation of two C-C bonds by reaction of aromatic or aliphatic Grignard reagents with (E)- or (Z)-1-bromo-2-phenylthioethene in the presence of nickel(II) or palladium(II) catalysts provides a novel stereospecific route to a variety of (E)- or (Z)-olefins of the R-CH=CH-R and R1-CH=CH-R2 type, with a stereoselectivity higher than 99percent for the (E) isomers and in the range 95-98percent for the (Z) isomers.
- Fiandanese, Vito,Marchese, Giuseppe,Naso, Francesco,Ronzini, Ludovico
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p. 647 - 649
(2007/10/02)
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