5296-64-0Relevant articles and documents
Size-dependent oxidation of monodisperse silicon nanocrystals with allylphenylsulfide surfaces
Rinck, Julia,Schray, Dirk,Kübel, Christian,Powell, Annie K.,Ozin, Geoffrey A.
, p. 335 - 340 (2015)
The synthesis and characterization of size-separated silicon nanocrystals functionalized with a heteroatom-substituted organic capping group, allylphenylsulfide, via photochemical hydrosilylation are described for the first time. These silicon nanocrystals form colloidally stable and highly photoluminescent dispersions in nonpolar organic solvents with an absolute quantum yield as high as 52% which is 20% above that of the allylbenzene analogue. Solutions of the size-separated fractions are characterized over time to monitor the effect of aging in air by following the change of their photoluminescence and absolute quantum yields, supplemented by transmission electron microscopy.
Synthesis of sulfimides and N-Allyl-N-(thio)amides by Ru(II)catalyzed nitrene transfer reactions of N-acyloxyamides
Zhang, Xinyu,Lin, Bo,Chen, Jianhui,Chen, Jiajia,Luo, Yanshu,Xia, Yuanzhi
supporting information, p. 819 - 825 (2021/02/01)
The N-acyloxyamides were employed as effective N-acyl nitrene precursors in reactions with thioethers under the catalysis of a commercially available Ru(II) complex, from which a variety of sulfimides were synthesized efficiently and mildly. If an allyl group is contained in the thioether precursor, the [2,3]-sigmatropic rearrangement of the sulfimide occurs simultaneously and the N-allyl-N-(thio)amides were obtained as the final products. Preliminary mechanistic studies indicated that the Ru-nitrenoid species should be a key intermediate in the transformation.
Iron(II) and Copper(I) Control the Total Regioselectivity in the Hydrobromination of Alkenes
Cruz, Daniel A.,Sinka, Victoria,De Armas, Pedro,Steingruber, Hugo Sebastian,Fernández, Israel,Martín, Víctor S.,Miranda, Pedro O.,Padrón, Juan I.
supporting information, p. 6105 - 6109 (2021/08/18)
A new method that allows the complete control of the regioselectivity of the hydrobromination reaction of alkenes is described. Herein, we report a radical procedure with TMSBr and oxygen as common reagents, where the formation of the anti-Markovnikov product occurs in the presence of parts per million amounts of the Cu(I) species and the formation of the Markovnikov product occurs in the presence of 30 mol % iron(II) bromide. Density functional theory calculations combined with Fukui's radical susceptibilities support the obtained results.
Yb(iii)-catalysedsyn-thioallylation of ynamides
Dutta, Shubham,Gandon, Vincent,Gogoi, Manash Protim,Mallick, Rajendra K.,Prabagar, B.,Sahoo, Akhila K.,Vanjari, Rajeshwer,Yang, Shengwen
supporting information, p. 7521 - 7524 (2021/08/05)
Reported herein is asyn-thioallylation of ynamides incorporating a sulfide moiety at the α-position and an allyl group at the β-position of the ynamide. The transformation is successful under ytterbium(iii)-catalysis, providing access to highly substituted thioamino-skipped-dienes with broad substrate scope. Thus, tetrasubstituted olefins (with four different functional groups: amide, phenyl, thioaryl/alkyl, and allyl on the carbon centers) are made in a single step from readily accessible ynamides, preserving complete atom economy. The reaction can be extended to the synthesis of selenoamino dienes by ynamidesyn-selenoallylation. DFT studies and control experiments provide insight into the reaction mechanism.
A mild and chemoselective CALB biocatalysed synthesis of sulfoxides exploiting the dual role of AcOEt as solvent and reagent
Anselmi, Silvia,Liu, Siyu,Kim, Seong-Heun,Barry, Sarah M.,Moody, Thomas S.,Castagnolo, Daniele
supporting information, p. 156 - 161 (2021/01/14)
A mild, chemoselective and sustainable biocatalysed synthesis of sulfoxides has been developed exploiting CALB and using AcOEt with a dual role of more environmentally friendly reaction solvent and enzyme substrate. A series of sulfoxides, including the drug omeprazole, have been synthesised in high yields and with excellent E-factors.
Air-stable binuclear Titanium(IV) salophen perfluorobutanesulfonate with zinc power catalytic system and its application to C–S and C–Se bond formation
Wang, Lingxiao,Qiao, Jie,Wei, Jiancong,Liang, Zhiwu,Xu, Xinhua,Li, Ningbo
, (2020/01/08)
An air-stable μ-oxo-bridged binuclear Lewis acid of titanium(IV) salophen perfluorobutanesulfonate [{Ti(salophen)H2O}2O][OSO2C4F9]2 (1) was successfully synthesized by the reaction of TiIV(salophen)Cl2 with AgOSO2C4F9 and characterized by techniques such as IR, NMR and HRMS. This complex was stable open to air over a year, and exhibited good thermal stability and high solubility in polar organic solvents. The complex also had relatively strong acidity with a strength of 0.8 Ho ≤ 3.3, and showed high catalytic efficiency towards various C–S and C–Se bond formations in the presence of zinc power. This catalytic system affords a mild and efficient approach to synthesis of thio- and selenoesters, α-arylthio- and seleno-carbonyl compounds, and thio- and selenoethers.
Sulfoxide synthesis from sulfinate esters under Pummerer-like conditions
Kobayashi, Akihiro,Matsuzawa, Tsubasa,Hosoya, Takamitsu,Yoshida, Suguru
, p. 5429 - 5432 (2020/06/04)
A facile synthetic method for the preparation of allyl sulfoxides byS-allylation of sulfinate esters proceeds through sulfonium intermediates without [3,3]-sigmatropic rearrangement and further Pummerer-type reactions of the resulting allyl sulfoxides. On the basis of the plausible reaction mechanism involving sulfonium salt intermediates,S-alkynylation andS-arylation were also accomplished.
One-pot Synthesis of Allyl Sulfides from Sulfinate Esters and Allylsilanes through Reduction of Alkoxysulfonium Intermediates
Hosoya, Takamitsu,Kobayashi, Akihiro,Matsuzawa, Tsubasa,Yoshida, Suguru
supporting information, p. 813 - 816 (2020/07/23)
An efficient method to synthesize allyl sulfides from sulfinate esters and allylsilanes is described. Based on the reactivity of isolated allyl(methoxy)phenyl sulfonium triflate, we have developed a simple one-pot method for the allyl sulfide synthesis by S-allylation of sulfinate esters and subsequent reduction with sodium borohydride. A number of allyl sulfides were prepared by this method leaving various functional groups unreacted.
Electrophilic Chlorine from Chlorosulfonium Salts: A Highly Chemoselective Reduction of Sulfoxides
Acosta-Guzmán, Paola,Mahecha-Mahecha, Camilo,Gamba-Sánchez, Diego
supporting information, p. 10348 - 10354 (2020/07/13)
Herein, we describe a selective late-stage deoxygenation of sulfoxides based on a novel application of chlorosulfonium salts and demonstrate a new process using these species generated in situ from sulfoxides as the source of electrophilic chlorine. The use of highly nucleophilic 1,3,5-trimethoxybenzene (TMB) as the reducing agent is described for the first time and applied in the deoxygenation of simple and functionalized sulfoxides. The method is easy to handle, economic, suitable for gram-scale operations, and readily applied for poly-functionalized molecules, as demonstrated with more than 45 examples, including commercial medicines and analogues. We also report the results of competition experiments that define the more reactive sulfoxide and we present a mechanistic proposal based on substrate and product observations.
Nickel phosphide nanoalloy catalyst for the selective deoxygenation of sulfoxides to sulfides under ambient H2pressure
Fujita, Shu,Mitsudome, Takato,Mizugaki, Tomoo,Yamaguchi, Sho,Yamasaki, Jun,Yamazoe, Seiji
supporting information, p. 8827 - 8833 (2020/11/23)
Exploring novel catalysis by less common, metal-non-metal nanoalloys is of great interest in organic synthesis. We herein report a titanium-dioxide-supported nickel phosphide nanoalloy (nano-Ni2P/TiO2) that exhibits high catalytic activity for the deoxygenation of sulfoxides. nano-Ni2P/TiO2 deoxygenated various sulfoxides to sulfides under 1 bar of H2, representing the first non-noble metal catalyst for sulfoxide deoxygenation under ambient H2 pressure. Spectroscopic analyses revealed that this high activity is due to cooperative catalysis by nano-Ni2P and TiO2. This journal is
