102680-02-4Relevant academic research and scientific papers
Alkenylation of C(sp3)?H Bonds by Zincation/Copper-Catalyzed Cross-Coupling with Iodonium Salts
Liu, Chuan,Wang, Qiu
supporting information, p. 4727 - 4731 (2018/03/21)
α-Vinylation of phosphonates, phosphine oxides, sulfones, sulfonamides, and sulfoxides has been achieved by selective C?H zincation and copper-catalyzed C(sp3)?C(sp2) cross-coupling reaction using vinylphenyliodonium salts. The vinylation transformation proceeds in high efficiency and stereospecificity under mild reaction conditions. This zincative cross-coupling reaction represents a general alkenylation strategy, which is also applicable for α-alkenylation of esters, amides, and nitriles in the synthesis of β,γ-unsaturated carbonyl compounds.
Efficient and selective sulfoxidation by hydrogen peroxide, using a recyclable flavin-[BMIm]PF6 catalytic system
Linden, Auri A.,Johansson, Mikael,Hermanns, Nina,Baeckvall, Jan-E.
, p. 3849 - 3853 (2007/10/03)
A new flavin catalyst 2 immobilized in an ionic liquid ([BMIm]PF 6) was used for the highly selective oxidation of sulfides to sulfoxides by hydrogen peroxide. The sulfoxides were obtained in good to high yields and high selectivity without any
Novel model sulfur compounds as mechanistic probes for enzymatic and biomimetic oxidations
Penenory, Alicia B.,Argueello, Juan E.,Puiatti, Marcelo
, p. 114 - 122 (2007/10/03)
To test for the intermediacy of sulfide radical cations in biomimetic and enzymatic oxidations, the sulfides PhSCH3 (1a), PhSCH2Ph (1b), PhSCHPh2 (1c), PhSCPh3 (1d), CH 3SCHPh2 (2), PhSCH2CH=CH2 (3), PhSCH2CH=CHPh (4) and CH3SCH2CH=CHPh (5) were studied, and their results were compared to those obtained for the corresponding chemical electron transfer (CET) and photoinduced electron transfer (PET) oxidations. The radical cations generated from 3-5 by CET in the presence of cerium(IV) ammonium nitrate (CAN) yielded only fragmentation products from the alkyl cations and the thiyl radicals (RS.), whereas 2.+ afforded both fragmentation and mainly α-deprotonation products. Photochemical treatment of the sulfides 1a and 1b with C(NO2) 4 gave only the corresponding sulfoxides, while fragmentation was the main pathway for the photoreactions of 1c, 2 and 5, and for 1d only this latter process was observed. These results support our selection of the sulfides RSCHPh2, RSCH2CH=CHPh (R = Me, Ph) and PhSCPh3 as models for the biomimetic and enzymatic studies. As evidenced by the sulfoxides and sulfones detected as unique products both in protic and in aprotic solvents, it is proposed that the mechanism of the biomimetic sulfoxidations of sulfides 1c and 2-5 by TPPFeIIICI is direct oxygen transfer. Three enzymes - Coprinus cinereus peroxidase (CiP), horseradish peroxidase (HRP) and chloroperoxidase (CPO) - were studied in the oxidation of sulfides 1a, 2, 4 and 5. The use of a racemic alkyl hydroperoxide in the CiP enzymatic oxidation of sulfides 5 and 2 yielded the corresponding sulfoxides (23 and 29%) and the aldehyde or benzophenone (5%), respectively. These results suggest the involvement of an ET process for the CiP-catalysed oxidation. Fragmentation products were observed in the enzymatic oxidation of sulfide 4 with HRP, which confirms the previously proposed ET mechanism. On the other hand, the CPO-enzymatic oxidation of sulfide 5 yielded only the corresponding sulfoxide, as would be expected for a direct oxygen-transfer or oxene mechanism. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.
Allylation with Pummerer-generated Subtituted Vinylthionium Ions
Hunter, Roger,Michael, Joseph P.,Simon, Clive D.,Walter, Daryl S.
, p. 9365 - 9376 (2007/10/02)
Pummerer-derived substituted vinylthionium ions (allyl phenyl sulfoxide, TMSOTf, EtN(i-Pr)2, CH2Cl2, -78 deg C) with a β-trimethylsilylmethyl (2), γ-phenyl (14), or γ-phenylthio (15) group allylate the enol silyl ethers of acetophenone (3) and cyclohexanone (4) in good yield.Allylation with (14) and (15) required slow addition of base in order to limit the rate of production of intermediate, and thus avoid unwanted sila-Pummerer type products.Huenigs's base conjugate addition was not observed in these cases.Both the (E)- and (Z)- forms of allyl sulfoxide (15) were shown to equilibrate to the (E)-transoid conformer prior to allylation resulting in exclusive (E)-vinyl sulfide formation.Blocking of the γ-position resulted in preferential α-attack.
Synthesis of 2-(Trimethylsilyl)ethyl Benzenesulfenate and Benzeneselenenate and Their Reaction with Some Electrophiles in the Presence of Tetrabutylammonium Fluoride
Oida, Tatsuo,Ohnishi, Atsushi,Shimamaki, Toshiharu,Hayashi, Yoshiyuki,Tanimoto, Shigeo
, p. 702 - 704 (2007/10/02)
2-(Trimethylsilyl)ethyl benzenesulfenate was allowed to react with several halides in the presence of tetrabutylammonium fluoride (TBAF) to afford the corresponding phenyl sulfoxides as the main product.In the reaction of 2-(trimethylsilyl)ethyl benzeneselenenate and several halides with TBAF, the corresponding alcohols were obtained as the main product.
STRUCTURAL EFFECTS UPON COMPETITIVE DECOMPOSITION PATHWAYS OF THIOSULFOXIDE INTERMEDIATES
Baechler, Raymond D.,Filippo, Lynn James San,Schroll, Alayne
, p. 5247 - 5250 (2007/10/02)
Mixtures of sulfides and disulfides are obtained upon reaction of boron trisulfide with a series of allyl aryl sulfoxides, with the product distributions dependent upon the structures of the intermediate thiosulfoxides.
