15436-04-1Relevant academic research and scientific papers
Regio- and stereospecific cleavage of stannylepoxides with lithium phenylsulfide
Cuadrado, Purificación,González-Nogal, Ana M.
, p. 8993 - 8996 (2001)
Unsubstituted and α or β C-substituted epoxystannanes react with lithium phenylsulfide to give regio- and stereodefined α-phenylthio-β-hydroxystannanes resulting from α-opening with inversion of configuration. On the other hand, α- or β-trans-silyl epoxys
Radical Cation Cycloadditions Using Cleavable Redox Auxiliaries
Lin, Shishi,Lies, Shane D.,Gravatt, Christopher S.,Yoon, Tehshik P.
supporting information, p. 368 - 371 (2017/04/21)
The incorporation of an easily oxidized arylsulfide moiety facilitates the photocatalytic generation of alkene radical cations that undergo a variety of cycloaddition reactions with electron-rich reaction partners. The sulfide moiety can subsequently be reductively cleaved in a traceless fashion, affording products that are not otherwise directly accessible using photoredox catalysis. This approach constitutes a novel oxidative “redox auxiliary” strategy that offers a practical means to circumvent a fundamental thermodynamic limitation facing photoredox reactions.
Nickel-catalyzed electrochemical synthesis of dihydro-berazo[b]thiophene derivatives
Pelletier, Jeremie,Olivero, Sandra,Dunach, Elisabet
, p. 3343 - 3348 (2007/10/03)
The intramolecular electrochemical reductive cyclization of orthohaloaryl allyl thioethers catalyzed by Ni(II) complexes associated to cyclam ligands affords dihydro-benzo[b]thiophene derivatives in moderate to good yields.
Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 15. Generation of alkoxycarbonyl(sulfenyl)carbenes and their intramolecular insertion to give alkenyl sulfides
Aitken, R. Alan,Armstrong, Jill M.,Drysdale, Martin J.,Ross, Fiona C.,Ryan, Bruce M.
, p. 593 - 604 (2007/10/03)
A range of 18 alkoxycarbonyl sulfinyl phosphorus ylides 9 have been prepared and their behaviour upon flash vacuum pyrolysis (FVP) at 600 deg C examined. For R1 = H, Me and Et they lose Ph3PO and in some cases Ph3P to give mixtures of products including the alkenyl sulfides 10, the sulfides 11, the disulfides 12 and the thioesters 14. The alkenyl sulfides 10 most likely arise from intramolecular insertion of the alkoxycarbonyl sulfenyl carbenes resulting from loss off Ph3PO to produce β-lactones which then lose CO2 and this is supported by the results from 13C labelled ylides. Possible mechanisms for the formation of 11 and 14 are also presented and the feasibility of various steps has been examined by preparation and pyrolysis of the proposed intermediates. In contrast, pyrolysis of the ylides 9 where R1 = Ph and the tert-butoxycarbonyl ylides 30 leads mainly to complete fragmentation with loss of Ph3PO and benzyl alcohol or 2-methylpropan-2-ol and does not give any useful sulfur-containing products. Four alkoxy-carbonyl sulfonyl diazo compounds 33 have been prepared and in three cases they give the alkenyl sulfones 34 upon FVP at 400 deg C, probably by an intramolecular insertion and decarboxylation process analogous to the formation of 10 from 9. On the other hand the alkoxycarbonyl carbenes produced by FVP of the amino acid-derived diazo compounds 35 undergo alternative proocesses with no sign of β-lactone formation. Fully assigned 13C NMR data are presented for 13 of the ylides.
First synthesis, X-ray structure analysis and reactions of alkenyltriphenylbismuthonium salts
Matano, Yoshihiro,Yoshimune, Masanori,Azuma, Nagao,Suzuki, Hitomi
, p. 1971 - 1977 (2007/10/03)
Treatment of triphenylbismuth difluoride with alkenyltrimethylsilanes 1 or trimethylsilyl cyanidealkenyltrialkylstannanes 3 in the presence of boron trifluoride-diethyl ether gave the corresponding alkenyltriphenylbismuthonium tetrafluoroborates 2 in moderate to good yields. An X-ray crystallographic analysis of the salt 2e confirmed the distorted tetrahedral geometry of the central bismuth atom. When treated with a sulfinate 5 or the thiolate 11, the salts 2 readily transferred both the vinyl and phenyl moieties to these nucleophiles to afford the sulfones 7-10 or the sulfides 12, 13, respectively. In the presence of a palladium catalyst, the salt 2e underwent the Heck-type reaction with ethyl acrylate 17 to afford the dienoate 18 and cinnamate 19 in moderate yields. Action of KOBut on the salt 2b yielded p-tolylacetylene 22, while a similar reaction with the salt 2e in the presence of the styrenes 23 gave the cyclopropanes 24. A Hammett study of the latter reaction has suggested a possible involvement of an alkylidenecarbene as the intermediate in these base-promoted reactions.
MONOALKYLATION AND MONOPHENYLATION OF ISOPROPYLTHIOPHENYL METHYL SELENIDES AND 2-PHENYLTHIOETHENYL METHYL SELENIDES WITH GRIGNARD REAGENTS PROMOTED BY LOW-VALENT NICKEL SPECIES. REGIO- AND STEREOSELECTIVE CLEAVAGE OF THE CARBON-SELENIUM BOND
Tingoli, Marco,Tiecco, Marcello,Testaferri, Lorenzo,Chianelli, Donatella
, p. 59 - 61 (2007/10/02)
The substitution of the methylselenium group in different (isopropylthio)phenyl and (phenylthio)ethenyl methyl selenides by alkyl and phenyl groups, through Grignard reaction mediated by phosphino-ligated nickel species, is described.In all cases this substitution occurs smoothly and at a rate which is fast enough to leave the C-S bond unaffected.In the olefinic series the use of a bidenate phosphine ligand on the nickel catalyst is required to promote the stereocontrolled cleavage of the C-Se bond in the case of the Z isomers.
Structure-Stability Relationships in Vinyl Sulfides. III. Stabilization Caused by Different Alkylthio and Phenylthio Groups Attached to an Olefinic Double Bond
Kimmelma, Reijo
, p. 550 - 555 (2007/10/02)
The stabilization energies of different alkylthio and phenylthio groups attached to an olefinic double bond have been evaluated with respect to the energy differences of the isomerization reactions of some unsaturated sulfides, in which the double bond migrates from the β,γ- to the α,β-position.According to these results the stabilization energies (in kJ mol-1) are: MeS 15.6, EtS 14.8, i-PrS 15.7, t-BuS 17.5 and PhS 14.4
HYDRIDE ABSTRACTION AND REGIOSELECTIVE INSERTION REACTION AT β C-H BOND OF ALKYLLITHIUM BY ETHYL(PHENYLTHIO)METHYLENE CARBENOID
Harada, Toshiro,Maeda, Hisatomo,Oku, Akira
, p. 6489 - 6492 (2007/10/02)
Study on the reaction of alkyllithium with 1-chloropropyl phenyl sulfide showed two novel reactions, the regioselective insertion and the hydride abstraction, at the β C-H bond of alkyllithium by ethyl(phenylthio)methylene carbenoid.
PREPARATION OF 1-ALKENYL PHENYL SULFIDES BY THE NICKEL(II)-COMPLEXES CATALYZED COUPLING REACTION OF 3-METHOXY-1-PHENYLTHIO-1-PROPENE WITH GRIGNARD REAGENTS
Sugimura, Hideyuki,Takei, Hisashi
, p. 1505 - 1508 (2007/10/02)
The reaction of on 3-methoxy-1-phenylthio-1-propene with aryl and primary alkyl Grignard reagents in the presence of nickel(II)-phosphine complex in benzene or toluene proceeded chemo- and regioselectively to give 1-alkenyl phenyl sulfides in high yields.
