32291-77-3Relevant academic research and scientific papers
E -Selective synthesis of vinyl sulfones via silver-catalyzed sulfonylation of styrenes
Gui, Qingwen,Han, Kang,Liu, Zhuoliang,Su, Zhaohong,He, Xiaoli,Jiang, Hongmei,Tian, Bufan,Li, Yangyan
, p. 5748 - 5751 (2018)
An efficient and highly E-selective protocol for the synthesis of vinyl sulfones is described. This simple protocol demonstrates the first synthesis of vinyl sulfones via a silver-catalyzed C-S bond coupling reaction. In addition, the success of the reaction was found to be critically dependent on the use of TEMPO as the additive.
Photocatalyst size controls electron and energy transfer: Selectable: e / Z isomer synthesis via C-F alkenylation
Singh,Fennell,Weaver
, p. 6796 - 6802 (2016)
Photocatalytic alkene synthesis can involve electron and energy transfer processes. The structure of the photocatalyst can be used to control the rate of the energy transfer, providing a mechanistic handle over the two processes. Jointly considering catalyst volume and emissive energy provides a highly sensitive strategy for predicting which mechanistic pathway will dominate. This model was developed en route to a photocatalytic Caryl-F alkenylation reaction of alkynes and highly-fluorinated arenes as partners. By judicious choice of photocatalyst, access to E- or Z-olefins was accomplished, even in the case of synthetically challenging trisubstituted alkenes. The generality and transferability of this model was tested by evaluating established photocatalytic reactions, resulting in shortened reaction times and access to complimentary Z-cinnamylamines in the photocatalytic [2 + 2] and C-H vinylation of amines, respectively. These results show that taking into account the size of the photocatalyst provides predictive ability and control in photochemical quenching events.
Stereoselective Synthesis of Z-α,β-Unsaturated Sulfones Using Peterson Reagents
Ando, Kaori,Wada, Tomohiro,Okumura, Miho,Sumida, Hiroshi
, p. 6026 - 6029 (2016/01/09)
New Peterson reagents were prepared by introducing alkyloxy groups on the silicon atom in order to fix the conformation of the sulfone anion. The reagents 1d and 1e reacted with a variety of aldehydes after the treatment with Li-base to give Z-α,β-unsaturated sulfones with up to >99:1 selectivity in good to excellent yields. For the reaction with aliphatic aldehydes, CPME (cyclopentyl methyl ether) is the choice of solvent, while DME (1,2-dimethoxyethane) gave higher selectivity for the reaction with aromatic aldehydes.
Silver(I)-mediated reaction of trimethylsilylated arylacetylenes with sulfonyl chlorides: Unexpected formation of vinyl sulfones
Deng, Gui Sheng,Sun, Teng Fei
, p. 1115 - 1118,4 (2020/08/20)
A novel reaction of trimethylsilylated arylacetylenes with sulfonyl chlorides was performed in the presence of silver nitrate or triflate. Conjugated vinyl sulfones as dramatic products were obtained in moderate yields and with Z-selectivity. A free radical mechanism has been proposed to account for the formation of the products.
Studies on hydrozirconation of 1-alkynyl sulfoxides or sulfones and the application for the synthesis of stereodefined vinyl sulfoxides or sulfones
Huang, Xian,Duan, Dehui,Zheng, Weixin
, p. 1958 - 1963 (2007/10/03)
The hydrozirconation reaction of 1-alkynyl sulfoxides or sulfones with CP2Zr(H)Cl in THF at room temperature predominantly gave Z-β-zirconated vinyl sulfoxides or sulfones with excellent regioselectivity. Compared with 1-alkynyl sulfoxides, the hydrozirconation reaction of 1-alkynyl sulfones exhibits great synthetic potential, leading to the efficient preparation of Z-β-halovinyl sulfones, Z-β-sulfonyl α,β-unsaturated ketones, and Z-β-alkynyl vinyl sulfones. Although the reaction mechanisms are still not clear, the neighboring group participation of the sulfinyl or sulfonyl group may be playing an important role in this unique hydrozirconation reaction.
A useful method for configuration assignement of vinyl sulfides; stereochemical reassessment of the radical addition of benzenethiol to alkynes
Benati, Luisa,Capella, Laura,Montevecchi, Pier Carlo,Spagnolo, Piero
, p. 1035 - 1038 (2007/10/02)
A comparative analysis of the 1H NMR spectra of (E)- and (Z)-phenyl and alkyl sulfides and their corresponding sulfones provides a useful method for establishing their configuration.Although by employing this method we generally confirm our previous configurational assignement for benzenethiol/alkyne adducts, those for (E)- and (Z)-3-(phenylsulfanyl)hex-3-ene and 4-phenylsulfanyl)oct-4-ene, are shown to have been assigned incorrectly.In the light of the present results it is concluded that radical addition of benzenethio to alkynes at 100 deg C generally proceeds with trans-selectivity.This conclusion is the reverse of our earlier claim for the effect that benzenethiol adds to terminal alkynes and alkylphenylacetylenes in a trans-stereoselective mode, but in a cis-stereoselective mode to dialkylacetylenes bearing (rather) bulky alkyl groups.
Reactions of Alkylmercurials with Heteroatom-Centered Acceptor Radicals
Russell, Glen A.,Ngoviwatchai, Preecha,Tashtoush, Hasan I.,Pla-Dalmau, Anna,Khanna, Rajive K.
, p. 3530 - 3538 (2007/10/02)
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.
A Free Radical Addition-Fragmentation Reaction for the Preparation of Vinyl Sulfones and Phosphine Oxides
Keck, Gary E.,Byers, Jeffrey H.,Tafesh, Ahmed M.
, p. 1127 - 1128 (2007/10/02)
A free radical chain process is reported which gives vinyl sulfones or phosphine oxides in good to moderate yields under nonreducing conditions; the reaction involves irradiation of appropriate precursors to carbon-centered radicals with β-tri-n-butylstan
Organic syntheses with sulfones No. XLII. Oxidation of α-sulfonyl carbanions with cupric salts.
Baudin, Jean-Bernard,Julia, Marc,Rolando, Christian,Verpeaux, Jean-Noael
, p. 493 - 497 (2007/10/02)
α-Lithiated phenylalkyl sulfones, on treatment with various cupric salts, give comparable amounts of the α,α'-dimer and the corresponding vinylic sulfone.With cupric acetate or propionate, dehydrogenation occurs selectively: primary sulfones are converted into α,β-unsaturated sulfones in high yield.
Preparation of Vinylic Sulphones by Peterson Olefination using Phenyl Trimethylsilylmethyl Sulphone
Craig, Donald,Ley, Steven V.,Simpkins, Nigel S.,Whitham, Gordon H.,Prior, Michael J.
, p. 1949 - 1952 (2007/10/02)
The anion generated from phenyl trimethylsilylmethyl sulphone using butyl-lithium in dimethoxyethane, readily reacts at -78 deg C with various carbonyl compounds to afford vinylic sulphones on work-up at room temperature.The reaction conditions are tolera
