6930-77-4Relevant academic research and scientific papers
The first observation of γ-sila-pummerer rearrangement
Mikina, Maciej
, p. 454 - 458 (2013)
2-Sulfinyl-3-trimethylsilylmethylcycloalkanones unexpectedly undergo γ-sila-Pummerer rearrangement. The first examples of this new type of rearrangement are presented.
Natural product inspired allicin analogs as novel anti-cancer agents
Bhaumik, Ishani,Pal, Kunal,Debnath, Utsab,Karmakar, Parimal,Jana, Kuladip,Misra, Anup Kumar
, p. 259 - 272 (2019/02/07)
A series of novel analogs of Allicin (S-allyl prop-2-ene-1-sulfinothioate) present in garlic has been synthesized in high yield. Synthesized 23 compounds were evaluated against different breast cancer cells (MDA-MB-468 and MCF-7) and non-cancer cells (WI38). Four compounds (3f, 3h, 3m and 3u) showed significant cytotoxicity against cancer cells whereas nontoxic to the normal cells. Based on the LD50 values and selectivity index (SI), compound 3h (S-p-methoxybenzyl (p-methoxyphenyl)methanesulfinothioate) was considered as most promising anticancer agent amongst the above three compounds. Further bio-chemical studies confirmed that compound 3h promotes ROS generation, changes in mitochondrial permeability transition and induced caspase mediated DNA damage and apoptosis.
One-pot synthesis of α-phenylsulfinyl ketones by reaction of phenyl benzenethiosulfinate with enolate anions, and synthesis of sulfoxides and sulfides by its reaction with Grignard reagents
Fakhry, Jerome,Grayson, David H.
, p. 556 - 563 (2017/12/28)
Phenyl benzenethiosulfinate reacts with enolate anions derived from ketones to give α-phenylsulfinyl ketones directly, together with minor amounts of α-phenylsulfanyl ketones. These are easily separated by forming the water-soluble sodium salts of the sulfinyl compounds. Grignard reagents also react with phenyl benzenethiosulfinate, to give mixtures of sulfoxides and sulfides.
Oxidation of disulfides to thiolsulfinates with hydrogen peroxide and a cyclic seleninate ester catalyst peroxide and a cyclic seleninate ester catalyst
McNeil, Nicole M. R.,McDonnell, Ciara,Hambrook, Miranda,Back, Thomas G.
, p. 10748 - 10762 (2015/08/11)
Cyclic seleninate esters function as mimetics of the antioxidant selenoenzyme glutathione peroxidase. They catalyze the reduction of harmful peroxides with thiols, which are converted to disulfides in the process. The possibility that the seleninate esters could also catalyze the further oxidation of disulfides to thiolsulfinates and other overoxidation products under these conditions was investigated. This has ramifications in potential medicinal applications of seleninate esters because of the possibility of catalyzing the unwanted oxidation of disulfide-containing spectator peptides and proteins. A variety of aryl and alkyl disulfides underwent facile oxidation with hydrogen peroxide in the presence of catalytic benzo-1,2-oxaselenolane Se-oxide affording the corresponding thiolsulfinates as the principal products. Unsymmetrical disulfides typically afforded mixtures of regioisomers. Lipoic acid and N,N′-dibenzoylcystine dimethyl ester were oxidized readily under similar conditions. Although isolated yields of the product thiolsulfinates were generally modest, these experiments demonstrate that the method nevertheless has preparative value because of its mild conditions. The results also confirm the possibility that cyclic seleninate esters could catalyze the further undesired oxidation of disulfides in vivo.
Silica-coated magnetite nanoparticles stabilized simple Mn-tetraphenylporphyrin for aqueous phase catalytic oxidations with tert-butyl hydroperoxide
Rezaeifard, Abdolreza,Farshid, Parisa,Jafarpour, Maasoumeh,Moghaddam, Gholamreza Kardan
, p. 9189 - 9196 (2014/03/21)
An economic and environmentally friendly system for efficient and selective oxidation of industrially and biologically important substrates in water using tert-butyl hydroperoxide catalyzed by a new magnetically recoverable Mn-porphyrin was developed. The easily prepared heterogeneous catalyst was characterized by powder X-ray diffraction, transmission electron microscopy, scanning electron microscopy, FT-IR and UV-vis spectroscopy. The size of the catalyst was estimated to be about 10 nm. The thermal gravimetric analysis demonstrated that the nanocatalyst was thermally stable up to almost 300 °C. The reactivity, selectivity and scope of the reaction were investigated with a variety of olefins, saturated hydrocarbons, alcohols and organosulfur compounds. The reactions proceeded smoothly in the absence of surfactants, organic co-solvents and thus take place "on water". The separation and recycling of nanocatalyst as well as isolation of water-insoluble products were simple, effective and economical in this clean oxidation method.
The sila-Pummerer reaction of γ-silyl substituted cycloalkanoyl sulfoxides: The first examples and a new approach to 3-substituted cycloalk-2-enones
Mikina, Maciej,Miko?ajczyk, Marian
, p. 3954 - 3956 (2014/07/08)
The thermal decomposition of 3-(α-trimethylsilyl)alkyl substituted 2-(phenylsulfinyl)cycloalkanones occurs via the γ-sila-Pummerer reaction, affording 3-substituted cycloalk-2-enones and unstable trimethylsilyl benzenesulfenate as an elimination by-product. The starting γ-silyl substituted cycloalkanoyl sulfoxides were obtained through the conjugate addition reaction of nucleophilic reagents to 2-(phenylsulfinyl)cycloalk-2- enones. The tandem conjugate addition/γ-sila-Pummerer reaction investigated here provides a new route to 3-substituted cycloalk-2-enones.
Structural effects on the C-S bond cleavage in aryl tert -butyl sulfoxide radical cations
Cavattoni, Tullio,Del Giacco, Tiziana,Lanzalunga, Osvaldo,Mazzonna, Marco,Mencarelli, Paolo
, p. 4886 - 4894 (2013/07/11)
The oxidation of a series of aryl tert-butyl sulfoxides (4-X-C 6H4SOC(CH3)3: 1, X = OCH 3; 2, X = CH3; 3, X = H; 4, X = Br) photosensitized by 3-cyano-N-methylquinolinium perchlorate (3-CN-NMQ+) has been investigated by steady-state irradiation and nanosecond laser flash photolysis (LFP) under nitrogen in MeCN. Products deriving from the C-S bond cleavage in the radical cations 1+?-4+? have been observed in the steady-state photolysis experiments. By laser irradiation, the formation of 3-CN-NMQ? (λmax = 390 nm) and 1 +?-4+? (λmax = 500-620 nm) was observed. A first-order decay of the sulfoxide radical cations, attributable to C-S bond cleavage, was observed with fragmentation rate constants (k f) that decrease by increasing the electron donating power of the arylsulfinyl substituent from 1.8 × 106 s-1 (4 +?) to 2.3 × 105 s-1 (1 +?). DFT calculations showed that a significant fraction of the charge is delocalized in the tert-butyl group of the radical cations, thus explaining the small substituent effect on the C-S bond cleavage rate constants. Via application of the Marcus equation to the kinetic data, a very large value for the reorganization energy (λ = 62 kcal mol-1) has been calculated for the C-S bond scission reaction in 1+?-4 +?.
A traceless, one-pot preparation of unsymmetric disulfides from symmetric disulfides through a repeated process involving sulfenic acid and thiosulfinate intermediates
Han, Minsoo,Lee, Jong Tak,Hahn, Hoh-Gyu
supporting information; experimental part, p. 236 - 239 (2011/02/28)
A variable group of unsymmetric disulfides was prepared under mild reaction conditions and in high yields through the reaction of symmetric disulfides with sulfuryl chloride followed by treatment with thiols in the presence of water.
Photosensitized oxidation of alkyl phenyl sulfoxides. C-S bond cleavage in alkyl phenyl sulfoxide radical cations
Baciocchi, Enrico,Del Giacco, Tiziana,Lanzalunga, Osvaldo,Mencarelli, Paolo,Procacci, Barbara
, p. 5675 - 5682 (2008/12/22)
(Chemical Equation Presented) The 3-cyano-N-methylquinolinium Perchlorate (3-CN-NMQ+ ClO4-)-photosensitized oxidation of phenyl alkyl sulfoxides (PhSOCR1R2R3,1, R1 = R2 = H, R3 = Ph; 2, R1 = H, R2 = Me, R3 = Ph; 3, R1 = R2 = Ph, R3 = H; 4, R1 = R2 = Me, R3 = Ph; 5, R1 = R2 = R3 = Me) has been investigated by steady-state irradiation and nanosecond laser flash photolysis (LFP) under nitrogen in MeCN. Steady-state photolysis showed the formation of products deriving from the heterolytic C-S bond cleavage in the sulfoxide radical cations (alcohols, R 1R2R3COH, and acetamides, R1R 2R3CNHCOCH3) accompanied by sulfur-containing products (phenyl benzenethiosulfinate, diphenyl disulfide, and phenyl benzenethiosulfonate). By laser irradiation, the formation of 3-CN-NMQ ? (λmax = 390 nm) and sulfoxide radical cations 1?+, 2?+, and 5?+ (λmax = 550 nm) was observed within the laser pulse. The radical cations decayed by first-order kinetics with a process attributable to the heterolytic C-S bond cleavage leading to the sulfinyl radical and an alkyl carbocation. The radical cations 3?+ and 4?+ fragment too rapidly, decaying within the laser pulse. The absorption band of the cation Ph2CH+ (λmax = 440 nm) was observed with 3 while the absorption bands of 3-CN-NMQ? and PhSO? (λmax = 460 nm) were observed just after the laser pulse in the LFP experiment with 4. No competitive β-C-H bond cleavage has been observed in the radical cations from 1-3. The C-S bond cleavage rates were measured for 1?+, 2?+, and 5?+. For 3?+ and 4?+, only a lower limit (ca. >3 × 107 s-1) could be given. Quantum yields (Φ) and fragmentation first-order rate constants (k) appear to depend on the structure of the alkyl group and on the bond dissociation free energy (BDFE) of the C-S bond of the radical cations determined by a thermochemical cycle using the C-S BDEs for the neutral sulfoxides 1-5 obtained by DFT calculations. Namely, Φ and k increase as the C-S BDFE becomes more negative, that is in the order 1 ?+ (1.4 × 106 s-1) with the upper limit (104 s-1) given for fert-butyl phenyl sulfide radical cation (Baciocchi, E.; Del Giacco, T.; Gerini, M. F.; Lanzalunga, O. Org. Lett. 2006, 8, 641-644). It turns out that sulfoxide radical cations undergo C-S bond breaking at a rate at least 2 orders of magnitude faster than that of corresponding sulfide radical cations.
