- A visible-light photocatalytic thiolation of aryl, heteroaryl and vinyl iodides
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The general catalytic synthesis of aryl and vinyl thioethers from readily available halides remains a challenge. Herein we report a unified method for the thiolation of aryl and vinyl iodides with dialkyl disulfides using visible light photoredox catalysis. A range of thioether products bearing diverse functional groups can be accessed in high yield and with excellent chemoselectivity. We demonstrate the versatility of this method through the expedient synthesis of a family of thioether-rich natural products. A detailed investigation of the photocatalytic mechanism is presented from both steady-state and time-resolved luminescent quenching as well as transient absorption spectroscopy experiments.
- Czyz,Weragoda,Monaghan,Connell,Brzozowski,Scully,Burton,Lupton,Polyzos
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supporting information
p. 1543 - 1551
(2018/03/08)
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- Cobalt modified N-doped carbon nanotubes for catalytic C=C bond formation via dehydrogenative coupling of benzyl alcohols and DMSO
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The development of heterogeneous, cost-effective and environmentally benign catalysts to construct C=C bonds is highly desirable. We report here Co@N-doped carbon nanotubes (Co@NCNT) as a catalyst for a novel synthesis of styryl sulfides via dehydrogenative coupling of benzyl alcohols and DMSO under anaerobic conditions. This reaction maintains high atom efficiency as the C=C bond is formed without the cracking of the C-S bond. We proposed that Co modified N-doped carbon sites are the active sites, different from traditionally believed metal centers for dehydrogenative C-C coupling. Moreover, the Co@NCNT catalyst could be easily separated and recycled for at least six runs. This work opens up a new application of metal-N-C catalysts in C=C bond-forming reactions in synthetic chemistry.
- Li, Jinlei,Liu, Guoliang,Shi, Lijun,Xing, Qi,Li, Fuwei
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supporting information
p. 5782 - 5788
(2017/12/26)
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- One-pot synthesis of alkyl styryl sulfides free from transition metal/ligand catalyst and thiols
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A new protocol for the one-pot synthesis of styryl alkyl sulfides was developed. This methodology involves the in situ generation of thiolate anions by nucleophilic substitution between potassium thioacetate and alkyl halides followed by fragmentation. Further reactions of these thiolate anions with substituted (E,Z)-β-styryl halides gave the corresponding sulfides with retention of stereochemistry in good to excellent yields. This procedure does not require a metal catalyst, it proceeds under mild conditions and in short times, and it is free from malodorous and air-sensitive alkyl thiols. Copyright
- Heredia, Adrian A.,Penenory, Alicia B.
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p. 991 - 997
(2013/03/14)
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- Regio- and stereoselective synthesis of 1,4-dienes
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Titanocene(ii)-promoted cross-coupling between (Z)-alkenyl methyl sulfones and terminal allenes produced 1,4-dienes regioselectively via the formation of 2-alkylidenetitanacyclopentanes. Preferential formation of E,Z-dienes was observed in the reaction us
- Oishi, Shigeki,Hatano, Keisuke,Tsubouchi, Akira,Takeda, Takeshi
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body text
p. 11639 - 11640
(2011/12/02)
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- Stereoconservative formation and reactivity of α-chalcogen- functionalized vinyllithium compounds from α-bromo-vinylic chalcogenides
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Bromine/lithium exchange was performed upon treatment of α-bromo-vinylic chalcogenides with butyllithium in hexane at room temperature to provide α-chalcogen-vinyllithium intermediates quantitatively. Addition of electrophiles to the lithiated compounds g
- Braga, Antonio L.,Zeni, Gilson,De Andrade, Leandro H.,Silveira, Claudio C.
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p. 595 - 596
(2007/10/03)
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- Chemistry of silyl thioketones. Part 10. Synthesis and reactivity of α-silyl vinyl sulfldes
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Aliphatic silyl thioketones containing an α-hydrogen atom undergo enethiolization to Z-α-silyl enethiols 2. Compounds 2 react with a variety of halides R3X to give open-chain α-silyl vinyl sulfides 3. Protiodesilylation of 3 was achieved upon treatment with fluoride ion to give vinyl sulfides 4. Reaction of 3 with Grignard reagents, in the presence of an appropriate nickel catalyst, results in a series of vinylsilanes 5 with a specific geometry.
- Bonini, Bianca Flavia,Comes-Franchini, Mauro,Fochi, Mariafrancesca,Mazzanti, Germana,Peri, Francesca,Ricci, Alfredo
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p. 2803 - 2809
(2007/10/03)
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- Selective synthesis of cis-α,β-unsaturated sulfoxides and sulfides by the Horner-Wittig reaction with bis(2,2,2-trifluoroethyl)phosphono sulfoxides and aromatic aldehydes
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cis-α,β-Unsaturated sulfoxides were predominantly formed in the Horner-Wittig reaction with bis(2,2,2-trifluoroethyl)phosphono sulfoxides and aromatic aldehydes, while the reaction of the corresponding sulfides showed trans- or lower cis-selectivity. The reduction of cis-α,β-unsaturated sulfoxides with tributylphosphine in carbon tetrachloride gave cis-vinyl sulfides with retention of stereochemistry.
- Kokin, Keisuke,Tsuboi, Shuji,Motoyoshiya, Jiro,Hayashi, Sadao
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p. 637 - 640
(2007/10/03)
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- Desulfonylation of α-Methylthio-α,β-unsaturated Sulfones. A New Route to One Carbon Homologation of Aromatic Aldehydes
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α-Methylthio-α,β-unsaturated sulfones 3 prepared from aromatic aldehydes 1 and sulfone 2 react with sodium hydrogen telluride in ethanol to undergo reductive desulfonylation to give vinyl sulfides 4 with certain extent of stereospecificity.A new route to one carbon homologation of aromatic aldehydes 1 to 5 is achieved by hydrolysis of 4 with titanium tetrachloride.
- Huang, Xian,Zhang, Han-Zhong
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- Ring Fragmentations of 2-Alkenyl- and 2-Benzyl-1,3-dithiolanes Induced by Bases. A Novel Method for the Preparation of 1,1-Bisalkylthio- or 1-Alkylthio-alk-1-enes and -alka-1,3-dienes
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The reaction of 2-alkenyl- and 2-benzyl-1,3-dithiolanes with several bases and successive alkylation with alkyl halides has been investigated.In the reaction of 2-alk-1-enyl-1,3-dithiolanes with organolithium reagents and alkyl halides, deprotonation at C
- Oida, Tatsuo,Tanimoto, Shigeo,Terao, Hiromu,Okano, Masaya
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p. 1715 - 1726
(2007/10/02)
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- COMPETITION BETWEEN VINYLIC SUBSTITUTION AND CONJUGATE ADDITION IN THE REACTIONS OF VINYL SELENOXIDES AND VINYL SELENONES WITH NUCLEOPHILES IN DMF
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Vinyl selenoxides and vinyl selenones present a different reactivity towards thiolate or alkoxide anions in DMF.In the case of selenoxides the addition of the nucleophiles regioselectively occurs at the α-carbon leading to the formation of the vinylic sub
- Tiecco, Marcello,Chianelli, Donatella,Testaferri, Lorenzo,Tingoli, Marco,Bartoli, Donatella
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p. 4889 - 4896
(2007/10/02)
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- NUCLEOPHILIC VINYLIC SUBSTITUTIONS ON UNACTIVATED SUBSTRATES. THE BEHAVIOUR OF STYRYL ALKYL SULPHIDES AND SELENIDES TOWARDS SULPHUR AND SELENIUM NUCLEOPHILES
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Sodium alkanethiolates or lithium methyl selenide react with styryl alkyl sulphides and selenides, in DMF at 100 deg C, to give the products of vinylic or aliphatic substitution.The two nucleophilic reagents are extremely selective.In the case of RSNa the
- Testaferri, L.,Tiecco, M.,Tingoli, M.,Chianelli, D.
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p. 1401 - 1408
(2007/10/02)
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