- copper(I) Species: Versatile Reagents To Prepare Functionally Substituted Allylic Silanes
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Smooth SN2' reactions in α-alkynyl and -allenyl oxiranes, in esters derived from α-allenic alcohols, and in the bis(methanesulfonate) derived from 1,4-dihydroxy-2-butyne were observed with the reagent copper(I).In this way, several allylic silanes bearing functional groups became available.Another route to functionally substituted allylic silanes was elaborated by adding copper(I) or its homocuprate derivative to alkynes such as 2-alkynoic esters, ethoxyacetylene, 1-alkynyl sulfides, and 1-alkynyl sulfones.The addition reactions appeared to occur regiospecifically and in many cases also with high stereoselectivity.A 1,4-bis-substituted butatriene derivative could be obtained by sequential addition of the biscuprate compound and methyl iodide to a 1-alkynyl sulfide.For one case it was shown that the addition of copper(I) to 1-alkynyl sulfones can be used to prepare sulfur-free 1-alkenes bearing in the β-position the (trimethylsilyl)methyl group.
- Kleijn, Henk,Vermeer, Peter
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- Anti-carbometalation of alkynyl sulfides using indium tribromide and ketene silyl acetals
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We developed the regioselective anti-carbometalation of alkynyl sulfides via the use of InBr3 and organosilicon nucleophiles to give β-mercaptoalkenylindium compounds. The structure of β-mercaptoalkenylindium was characterized by X-ray crystallographic analysis. A variety of disubstituted alkenyl sulfides were regio- and stereoselectively obtained by either halogenation or Pd-catalyzed cross-coupling with aryl halides using the mercaptoalkenylindiums.
- Kang, Kyoungmin,Nishimoto, Yoshihiro,Sakamoto, Kosuke,Yasuda, Makoto
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p. 1136 - 1139
(2020/10/06)
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- Gold-Catalyzed Oxidation of Thioalkynes to Form Phenylthio Ketene Derivatives via a Noncarbene Route
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Gold-catalyzed oxidations of thioalkynes with 8-methylquinoline oxides afford 2-phenylthioketenes that can be trapped efficiently with alcohols. The synthetic utility is manifested by terminal and internal thioalkynes over a wide scope, bearing esters, ke
- Sharma, Pankaj,Singh, Rahulkumar Rajmani,Giri, Sovan Sundar,Chen, Liang-Yu,Cheng, Mu-Jeng,Liu, Rai-Shung
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supporting information
p. 5475 - 5479
(2019/08/01)
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- Synthesis of aryl α,α-difluoroethyl thioethers a novel structure motif in organic chemistry, and extending to aryl α,α-difluoro oxyethers
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A method for the preparation of aryl α,α-difluoroethyl thioethers (ArSCF2CH3) is reported and the synthesis approach is extended to aryl α,α-difluoroethyl oxygen ethers. Selected building blocks are further elaborated in cross-coupli
- Tomita, Ren,Al-Maharik, Nawaf,Rodil, Andrea,Bühl, Michael,O'Hagan, David
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p. 1113 - 1117
(2018/02/22)
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- Synthesis of Terminal Ethynyl Aryl Selenides and Sulfides Based on the Retro-Favorskii Reaction of Hydroxypropargyl Precursors
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The retro-Favorskii reaction is an excellent way to achieve terminal alkynes. Methodologies that connect the synthesis of terminal alkynes and organochalcogen motifs are important for the construction of novel compounds. Fourteen new terminal alkynes containing either Csp?S or Csp?Se bonds were selectively prepared through the retro-Favorskii reaction from the respective carbinol precursors. It was discovered that terminal chalcogen alkynes were stable for weeks if stored as a solution in hexanes.
- Lopes, Eric F.,Dalberto, Bianca T.,Perin, Gelson,Alves, Diego,Barcellos, Thiago,Lenard?o, Eder J.
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supporting information
p. 13760 - 13765
(2017/09/08)
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- Fluorovinyl Thioethers as Putative Steric and Electronic Thioester Enolate Mimetics: Chemoselective HF Addition to Acetylene Thioethers
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Fluorovinyl thioethers are presented as a putative biomimetic surrogate for the enol/ate of a thioester. A method is explored for the preparation of fluorovinyl thioethers by treatment of acetylene thioethers with pyridinium (poly)-hydrogen fluoride. Titr
- Bello, Davide,Cormanich, Rodrigo A.,O'Hagan, David
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- Chiral propargylic cations as intermediates in SN1-type reactions: Substitution pattern, nuclear magnetic resonance studies, and origin of the diastereoselectivity
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Nine propargylic acetates, bearing a stereogenic center (-C*HXR 2) adjacent to the electrophilic carbon atom, were prepared and subjected to SN1-type substitution reactions with various silyl nucleophiles employing bismuth trifluoromethanesulfonate [Bi(OTf)3] as the Lewis acid. The diastereoselectivity of the reactions was high when the alkyl group R2 was tertiary (tert-butyl), irrespective of the substituent X. Products were formed consistently with a diastereomeric ratio larger than 95:5 in favor of the anti-diastereoisomer. If the alkyl substitutent R2 was secondary, the diastereoselectivity decreased to 80:20. The reaction was shown to proceed stereoconvergently, and the relative product configuration was elucidated. The reaction outcome is explained by invoking a chiral propargylic cation as an intermediate, which is preferentially attacked by the nucleophile from one of its two diastereotopic faces. Density functional theory (DFT) calculations suggest a preferred conformation in which the group R2 is almost perpendicular to the plane defined by the three substituents at the cationic center, with the nucleophile approaching the electrophilic center opposite to R2. Transition states calculated for the reaction of allyltrimethylsilane with two representative cations support this hypothesis. Tertiary propargylic cations with a stereogenic center (-C* HXR2) in the α position were generated by ionization of the respective alcohol precursors with FSO3H in SO2ClF at -80 C. Nuclear magnetic resonance (NMR) spectra were obtained for five cations, and the chemical shifts could be unambiguously assigned. The preferred conformation of the cations as extracted from nuclear Overhauser experiments is in line with the preferred conformation responsible for the reaction of the secondary propargylic cations.
- Nitsch, Dominik,Huber, Stefan M.,Poethig, Alexander,Narayanan, Arjun,Olah, George A.,Prakash, G. K. Surya,Bach, Thorsten
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supporting information
p. 2851 - 2857
(2014/03/21)
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- Facile 1,1-carboboration reactions of acetylenic thioethers
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The acetylenic thioether PhSCi - CSPh undergoes a rapid 1,1-carboboration reaction with facile -SPh migration upon treatment with B(C6F5)3 to yield the borylated ketene dithioacetal product (PhS)2C=C(C6/su
- Eller, Christina,Kehr, Gerald,Daniliuc, Constantin G.,Froehlich, Roland,Erker, Gerhard
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p. 384 - 386
(2013/03/14)
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- Regiocontrolled synthesis of ring-fused thieno[2,3-c]pyrazoles through 1,3-dipolar cycloaddition of nitrile imines with sulfur-based acetylenes
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1,3-Dipolar cycloadditions of C-carboxymethyl-N-arylnitrile imines with substituted acetylenes bearing thiol or sulfone groups were studied. The sulfur controls the regiochemistry of the reaction, and this protocol was applied to the synthesis of ring-fus
- Chandanshive, Jay Zumbar,Bonini, Bianca Flavia,Gentili, Denis,Fochi, Mariafrancesca,Bernardi, Luca,Franchini, Mauro Comes
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experimental part
p. 6440 - 6447
(2011/01/13)
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- Studies related to the total synthesis of the sesquiterpene core of the pyrrolobenzoxazine natural products CJ-12662 and CJ-12663
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A highly effective procedure is reported to synthesize a substituted bicyclo[4.2.0]octenol derivative by regioselective cycloaddition of phenyl-1-propynyl sulfide with cyclohexenone followed by selective reduction of the ketone group and reductive elimina
- Commandeur, Ma?gorzata,Commandeur, Claude,Paolis, Michael De,Edmunds, Andrew J.F.,Maienfisch, Peter,Ghosez, Léon
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scheme or table
p. 3359 - 3362
(2009/08/17)
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- Reactivity of 1-phenylsulfinyl-2-phenylsulfanylethylene (SOSE) with O-nucleophiles generated by potassium tert-butoxide
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E-1-Phenylsulfinyl-2-phenylsulfanylethylene (E-SOSE) reacts with O-nucleophiles generated by means of t-BuOK via an addition-elimination mechanism, thus affording the product of substitution of the phenylsulfanyl group in a stereo-conservative process. When used alone, the strongly basic and hindered tert-butoxide brings about elimination of either the phenylthiolate or phenylsulfinate groups. Z-SOSE is much more prone to elimination: either with t-BuOK alone or with other O-nucleophiles generated by t-BuOK, it always leads to products derived from elimination. Other alkaline tert-butoxides or other bases appear not as effective in generating species nucleophilic enough to react with E-SOSE.
- Pellizzaro, Leonardo,Cabianca, Elena,Tatibou?t, Arnaud,Padovan, Pierluigi,Fabris, Fabrizio,Rollin, Patrick,De Lucchi, Ottorino
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p. 3699 - 3703
(2008/02/09)
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- Reactivity of individual organolithium aggregates: A RINMR study of n-butyllithium and 2-methoxy-6-(methoxymethyl)phenyllithium
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Low-temperature rapid injection NMR (RINMR) experiments were performed on two lithium reagents, n-butyllithium and 2-methoxy-6-(methoxymethyl)phenyllithium (5), with the goal of measuring the relative reactivity of the different aggregates (dimer, mixed dimer, and tetramer for n-BuLi, monomer and tetramer for 5) toward typical electrophiles. The reaction of the n-BuLi dimer with (trimethylsilyl)acetylene first forms the mixed dimer n-BuLi·Me3SiC≡CLi, which is about 1/60 as reactive as the n-BuLi homodimer. The tetramer does not react. In the deprotonation of (phenylthio)acetylene, the n-BuLi dimer was found to be 3.5 × 108 as reactive as the tetramer, and in the addition to p-diethylaminobenzaldehyde, the relative reactivity was at least 2 × 104. In the deprotonation of (p-tolylsulfonyl)acetylene, the monomer of 5 was at least 1014 times as reactive as the tetramer. These measurements show that the difference in reactivity between the lower and higher aggregates of organolithium reagents can be many orders of magnitude higher than all previous estimates. Copyright
- Jones, Amanda C.,Sanders, Aaron W.,Bevan, Martin J.,Reich, Hans J.
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p. 3492 - 3493
(2008/01/01)
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- Homolytic carbostannylation of alkenes and alkynes with tributylstannyl enolates
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matrix presented In the presence of AIBN, tributylstannyl enolates derived from aromatic ketones reacted with electron-deficient alkenes and a variety of alkynes to give the corresponding carbostannylated adducts. The reactions with methyl acrylate gave α-tributylstannylmethyl-γ-ketoesters, unlike the known Michael-type reaction of stannyl enolates forming δ-ketoesters. The carbostannylation of alkynes proceeded in an anti addition mode to afford β,γ-unsaturated ketones. The reactivity of stannyl enolates as radical transfer agents could be utilized for radical cyclization of 1,6-enynes.
- Miura, Katsukiyo,Saito, Hiroshi,Fujisawa, Naoki,Wang, Di,Nishikori, Hisashi,Hosomi, Akira
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p. 4055 - 4057
(2007/10/03)
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- A non-outer sphere mechanism for the ionization of aryl vinyl sulfides by triarylaminium salts
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Evidence is presented that the formation of aryl vinyl sulfide cation radicals from the corresponding neutral precursors via reaction with tris(4- bromophenyl)aminium hexachloroantimonate in the context of a cation radical Diels-Alder addition to 1,3-cyclopentadiene does not occur via outer sphere electron transfer but by a mechanism involving strong covalent interaction between the aminium salt acting as an electrophile and the aryl vinyl sulfide substrate acting as a nucleophile.
- Bauld, Nathan L.,Aplin, J. Todd,Yueh, Wang,Loinaz, Ainhoa
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p. 11381 - 11389
(2007/10/03)
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- Phenylthioacetylene
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A two-step synthesis of phenylthioacetylene from thiophenol and methoxymethylene Meldrum's acid (2,2-dimethyl-1,3-dioxane-4,6-dione) is described.
- Hunter,McNab
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p. 1067 - 1068
(2007/10/02)
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- Dithio and Thiono Esters, 50. - α,β-Acetylenic Thioamides, Dithio Esters, and Thiono Esters
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α,β-Acetylenic amides 5 and thioamides 7 have been obtained by a palladium-catalysed condensation of the terminal acetylenes 3 with N,N-dimethylcarbamoyl chloride (4) or -thiocarbamoyl chloride (6).Sulfhydrolysis of the α,β-acetylenic thioamidium salts 19
- Hartke, Klaus,Gerber, Hans-Dieter,Roesrath, Ulrich
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p. 903 - 916
(2007/10/02)
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- Diastereoselective heteroconjugate addition of acetylenic derivatives
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Phenylthioacetylene, as its lithium acetylide, was used for opening of epoxides to afford homopropargyl alcohols. Hydrosilylation of these acetylenes were followed by oxidation to afford the corresponding silylvinyl sulfones, the electrophile in the heter
- Herunsalee,Isobe,Goto
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p. 3727 - 3736
(2007/10/02)
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- A Highly Selective Synthesis of Versatile (E)-1-Phenylthio Vinylstannanes
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An efficient, palladium-catalyzed hydrostannation of 1-phenylthio-1-alkynes 1 is described.This novel tributyltin hydride addition provides versatile 1-phenylthio vinylstannanes 2 regio- and stereoselectively.Key Words: Hydrostannylation; Palladium(0); Tr
- Magriotis, Plato A.,Brown, John T.,Scott, Mary E.
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p. 5047 - 5050
(2007/10/02)
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- Stereoselective construction and synthetic applications of phenylthio substituted iodoolefins
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(E)- and (Z)-Phenylthio substituted iodoolefins 1 and 2 have been synthesized stereoselectively via lower order stannylcuprate addition to and hydroalumination of appropriate alkyne precursors. Their utility in model studies on the synthesis of calichemic
- Magriotis,Doyle,Kim
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p. 2541 - 2544
(2007/10/02)
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- NUCLEOPHILIC REACTION AT A VINYL CENTER. XXII. SYNTHESIS AND NUCLEOPHILIC VINYLIC SUBSTITUTION IN E-β-FLUOROVINYL ARYL SULFONES
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The reaction of potassium fluoride with E-β-bromovinyl aryl sulfones in the presence of 18-crown-6-ether leads to a mixture of the sulfones XC6H4SO2CH2CHF2 and E-XC6H4SO2CH=CHF, the ratio of which decreases in the order X=CH3, H, Cl, NO2.The kinetics of n
- Shainyan, B. A.,Mirskova, A. N.
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- ALKYNE-COBALT COMPLEXES AS PROSTAGLANDIN SYNTHONS. IV. A POSSIBLE APPROACH VIA 2-PHENYLTHIOCYCLOPENT-2-ENONE.
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The effectiveness of (phenylthioethyne)hexacarbonyldicobalt as a precursor of mono, di- and tricyclic 2-phenylthiocyclopent-2-en-1-ones is demonstrated.These ketones are shown to undergo the expected 1,4-additions of mixed cuprate reagents, but further elaboration of the products to prostaglandin analogues was not pursued when models of the required alkylation reactions were found to proceed very poorly.
- Daalman, Lachlan,Newton, Roger F.,Pauson, Peter L.,Wadsworth, Alan
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p. 3150 - 3164
(2007/10/02)
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- SYNTHESES AND REACTIONS OF PHENYLTHIO AND PROPYLTHIOACETYLENIC COMPOUNDS
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Reactions of 2,2-dichlorovinyl sulfides and their sulfoxide and sulfone derivatives with tert-butoxide and with organolithium compounds have provided entries to chloroethynyl sulides, tert-butoxyethynyl sulfides and their derivatives.Application of these reactions for the synthesis of several functional derivatives is also described.Keywords: 2,2-dichlorovinyl sulfide; chloroethynyl sulfide; tert-butoxyethynyl sulfide; ethynyl sulfide; cyclobutenone
- Nagashima, Enkou,Suzuki, Kunio,Sekiya, Minoru
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p. 1274 - 1279
(2007/10/02)
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