618-41-7Relevant articles and documents
Carbanion reactivity - σ-adduct formation and elimination in the reactions of the carbanion from bis(phenylsulfonyl)methane with 4-nitrobenzofurazan derivatives
Asghar, Basim H.M.,Crampton, Michael R.,Isanbor, Chukwuemeka
, p. 225 - 229 (2008)
1H NMR studies in [2H6]-DMSO show that the carbanion. 4 from bis(phenylsulfonyl)methane reacts with 4,6- dinitrobenzofuroxan to yield a σ-adduct that undergoes base-catalysed elimination to yield an alkene derivative. Rate constants, measured spectrophotometrically, are reported for the corresponding reactions in methanol of 4 with 4-nitrobenzofurazan and some derivatives that give adducts at the 5-position. The intrinsic rate constant, ko, for this process has a value of 1.5±0.5. The 5-adducts undergo methoxide-catalysed elimination of phenylsulfinic acid to yield alkene derivatives and rate constants for this process are reported.
Photoredox Catalyzed Sulfonylation of Multisubstituted Allenes with Ru(bpy)3Cl2 or Rhodamine B
Chen, Jingyun,Chen, Shufang,Jiang, Jun,Lu, Qianqian,Shi, Liyang,Xu, Zekun,Yimei, Zhao
supporting information, (2021/11/09)
A highly regio- and stereoselective sulfonylation of allenes was developed that provided direct access to α, β-substituted unsaturated sulfone. By means of visible-light photoredox catalysis, the free radicals produced by p-toluenesulfonic acid reacted with multisubstituted allenes to obtain Markovnikov-type vinyl sulfones with Ru(bpy)3Cl2 or Rhodamine B as photocatalyst. The yield of this reaction could reach up to 91%. A series of unsaturated sulfones would be used for further transformation to some valuable compounds.
Abiological catalysis by myoglobin mutant with a genetically incorporated unnatural amino acid
Chand, Subhash,Ray, Sriparna,Yadav, Poonam,Samanta, Susruta,Pierce, Brad S.,Perera, Roshan
, p. 1795 - 1808 (2021/05/21)
To inculcate biocatalytic activity in the oxygen-storage protein myoglobin (Mb), a genetically engineered myoglobin mutant H64DOPA (DOPA = L-3,4-dihydroxyphenylalanine) has been created. Incorporation of unnatural amino acids has already demonstrated their ability to accomplish many non-natural functions in proteins efficiently. Herein, the presence of redox-active DOPA residue in the active site of mutant Mb presumably stabilizes the compound I in the catalytic oxidation process by participating in an additional hydrogen bonding (H-bonding) as compared to the WT Mb. Specifically, a general acid-base catalytic pathway was achieved due to the availability of the hydroxyl moieties of DOPA. The reduction potential values of WT (E° = -260 mV) and mutant Mb (E° = -300 mV), w.r.t. Ag/AgCl reference electrode, in the presence of hydrogen peroxide, indicated an additional H-bonding in the mutant protein, which is responsible for the peroxidase activity of the mutant Mb. We observed that in the presence of 5 mM H2O2, H64DOPA Mb oxidizes thioanisole and benzaldehyde with a 10 and 54 folds higher rate, respectively, as opposed to WT Mb. Based on spectroscopic, kinetic, and electrochemical studies, we deduce that DOPA residue, when present within the distal pocket of mutant Mb, alone serves the role of His/Arg-pair of peroxidases.
Photocatalytic α-Tertiary Amine Synthesis via C?H Alkylation of Unmasked Primary Amines
Alder, Catherine M.,Ballantyne, George,Cresswell, Alexander J.,Cunningham, William B.,Edwards, Lee J.,Grayson, Matthew N.,Kinsella, Anna G.,McKay, Blandine S. J.,Mules, Tom,Ryder, Alison S. H.,Turner-Dore, Jacob
supporting information, p. 14986 - 14991 (2020/06/20)
A practical, catalytic entry to α,α,α-trisubstituted (α-tertiary) primary amines by C?H functionalisation has long been recognised as a critical gap in the synthetic toolbox. We report a simple and scalable solution to this problem that does not require any in situ protection of the amino group and proceeds with 100 percent atom-economy. Our strategy, which uses an organic photocatalyst in combination with azide ion as a hydrogen atom transfer (HAT) catalyst, provides a direct synthesis of α-tertiary amines, or their corresponding γ-lactams. We anticipate that this methodology will inspire new retrosynthetic disconnections for substituted amine derivatives in organic synthesis, and particularly for challenging α-tertiary primary amines.
Visible-Light-Induced Radical Cascade Cyclizations of 1,7-Enynes with Sulfinic Acids: Direct Access to Sulfonated Chromanes and Sulfonated Tetrahydroquinolines under Metal-Free Conditions
Liu, Qi,Mei, Yousheng,Wang, Lei,Ma, Yongmin,Li, Pinhua
supporting information, p. 5669 - 5680 (2020/10/28)
Visible-light-induced strategy to access sulfonated chromanes and sulfonated 1,2,3,4-tetrahydroquinolines via a radical cascade cyclization of 1-(arylethynyl)-2-(vinyloxy)benzenes and N-allyl-2-(arylethynyl)anilines with aromatic and aliphatic sulfinic acids has been developed. In the presence of TBHP (7.5 mol%) as an oxidant and Eosin Y (3.0 mol%) as a photocatalyst, the reactions undergo smoothly to afford the corresponding products in good yields at room temperature under metal-free conditions. This transformation features low loading of TBHP, mild reaction conditions, simple operation, broad functional-group tolerance, and good yields of products. (Figure presented.).
Insights into the electrochemical degradation of sulfamethoxazole and its metabolite by Ti/SnO2-Sb/Er-PbO2 anode
Wang, Yanping,Zhou, Chengzhi,Wu, Jinhua,Niu, Junfeng
supporting information, p. 2673 - 2677 (2020/06/01)
Electrochemical degradation of sulfamethoxazole (SMX) and its metabolite acetyl-sulfamethoxazole (Ac-SMX) by Ti/SnO2-Sb/Er-PbO2 were investigated. Results indicated that the electrochemical degradation of SMX and Ac-SMX followed pseu
A Structural and Functional Model for the Tris-Histidine Motif in Cysteine Dioxygenase
Anandababu, Karunanithi,Ramasubramanian, Ramamoorthy,Wadepohl, Hubert,Comba, Peter,Johnee Britto, Neethinathan,Jaccob, Madhavan,Mayilmurugan, Ramasamy
, p. 9540 - 9547 (2019/07/04)
The iron(II) complexes [Fe(L)(MeCN)3](SO3CF3)2 (L are two derivatives of tris(2-pyridyl)-based ligands) have been synthesized as models for cysteine dioxygenase (CDO). The molecular structure of one of the complexes exhibits octahedral coordination geometry and the Fe?Npy bond lengths [1.953(4)–1.972(4) ?] are similar to those in the Cys-bound FeII-CDO; Fe?NHis: 1.893–2.199 ?. The iron(II) centers of the model complexes exhibit relatively high FeIII/II redox potentials (E1/2=0.988–1.380 V vs. ferrocene/ferrocenium electrode, Fc/Fc+), within the range for O2 activation and typical for the corresponding nonheme iron enzymes. The reaction of in situ generated [Fe(L)(MeCN)(SPh)]+ with excess O2 in acetonitrile (MeCN) yields selectively the doubly oxygenated phenylsulfinic acid product. Isotopic labeling studies using 18O2 confirm the incorporation of both oxygen atoms of O2 into the product. Kinetic and preliminary DFT studies reveal the involvement of an FeIII peroxido intermediate with a rhombic S= (Formula presented.) FeIII center (687–696 nm; g≈2.46–2.48, 2.13–2.15, 1.92–1.94), similar to the spectroscopic signature of the low-spin Cys-bound FeIIICDO (650 nm, g≈2.47, 2.29, 1.90). The proposed FeIII peroxido intermediates have been trapped, and the O?O stretching frequencies are in the expected range (approximately 920 and 820 cm?1 for the alkyl- and hydroperoxido species, respectively). The model complexes have a structure similar to that of the enzyme and structural aspects as well as the reactivity are discussed.
Allyl sulfone compound and preparation method and application thereof
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Paragraph 0043-0048, (2020/01/12)
The invention discloses an allyl sulfone compound and a preparation method and application thereof. The preparation method comprises the following steps of sequentially adding allyl alcohol, sulfinicacid, palladium tetrakis(triphenylphosphine) and calcium bis(trifluoromethylsulfonyl)imide into a reaction solvent in an inert gas atmosphere, and carrying out a reaction under stirring for 12-48 h atthe temperature of 30 DEG C, wherein the equivalent ratio of allyl alcohol, sulfinic acid, palladiumtetrakis(triphenylphosphine) and calcium bis(trifluoromethylsulfonyl)imide is 1: (1.5-2): (1-3%): (5-10%); and removing the reaction solvent in the reaction liquid, and then performingpurifying to obtain the allyl sulfone compound. The preparation method disclosed by the invention is high in economy and wide in applicable substrate range; in addition, the obtained allyl sulfone compound has potential pharmaceutical activity and biological activity and is an important skeleton widely existing inbiologically and pharmaceutically active molecules.
Synergistic combination of visible-light photo-catalytic electron and energy transfer facilitating multicomponent synthesis of β-functionalized α,α-diarylethylamines
Wu, Yanan,Zhang, Yipin,Jiang, Mingjie,Dong, Xunqing,Jalani, Hitesh B.,Li, Guigen,Lu, Hongjian
, p. 6405 - 6408 (2019/06/07)
A synthetic strategy with the visible-light photo-catalytic synergistic combination of electron and energy transfer processes has been developed. The mild reaction conditions allow the radical-radical cross-coupling phenomenon for the multicomponent synthesis of β-arylsulfonyl(diarylphosphinoyl)-α,α-diarylethyl-amines from readily available arylsulfinic acids (diarylphosphine oxides), 1,1-diarylethylenes and arylazides.
Reductive Cleavage of Secondary Sulfonamides: Converting Terminal Functional Groups into Versatile Synthetic Handles
Fier, Patrick S.,Kim, Suhong,Maloney, Kevin M.
supporting information, p. 18416 - 18420 (2019/11/20)
Sulfonamides are pervasive in pharmaceuticals and agrochemicals, yet they are typically considered as terminal functional groups rather than synthetic handles. To enable the general late-stage functionalization of secondary sulfonamides, we have developed a mild and general method to reductively cleave the N-S bonds of sulfonamides to generate sulfinates and amines, components which can further react in situ to access a variety of other medicinally relevant functional groups. The utility of this platform is highlighted by the selective manipulation of several complex bioactive molecules.
