14418-84-9Relevant academic research and scientific papers
Remote Site-Specific Radical Alkynylation of Unactivated C-H Bonds
Wang, Lin,Xia, Yong,Bergander, Klaus,Studer, Armido
, p. 5817 - 5820 (2018)
A method for remote radical C-H alkynylation at unactivated sites is reported. C-H functionalization proceeds via 1,5-hydrogen atom transfer (HAT) to amidyl radicals that are generated via an addition/fragmentation reaction. The readily installed N-allylsulfonyl moiety is used as a precursor of the N-centered radical. Unactivated secondary and tertiary as well as selected primary C-H bonds can be functionalized by this method.
Site-Selective Remote Radical C?H Functionalization of Unactivated C?H Bonds in Amides Using Sulfone Reagents
Xia, Yong,Wang, Lin,Studer, Armido
, p. 12940 - 12944 (2018)
A general and practical strategy for remote site-selective functionalization of unactivated aliphatic C?H bonds in various amides by radical chemistry is introduced. C?H bond functionalization is achieved by using the readily installed N-allylsulfonyl moiety as an N-radical precursor. The in situ generated N-radical engages in intramolecular 1,5-hydrogen atom transfer to generate a translocated C radical which is subsequently trapped with various sulfone reagents to afford the corresponding C?H functionalized amides. The generality of the approach is documented by the successful remote C?N3, C?Cl, C?Br, C?SCF3, C?SPh, and C?C bond formation. Unactivated tertiary and secondary C?H bonds, as well as activated primary C?H bonds, can be readily functionalized by this method.
Solvent-free, metal-free, aza-prins cyclization: Unprecedented access to δ-sultams
Clarisse, Damien,Pelotier, Béatrice,Fache, Fabienne
, p. 857 - 860 (2013)
Aza-Prins and the pauper: Aza-Prins cyclization between γ,δ-unsaturated tosylamines and aldehydes was successfully performed under solvent-free and metal-free conditions. When applied to β,γ-unsaturated sulfonamides, the corresponding δ-sultams were isolated in good yields (see scheme). This approach constitutes a new route to cyclic sulfonamides. Copyright
Ring closing metathesis and metal-catalyzed cyclopropanation for the preparation of sultone derivatives
Ali, Korany A.,Metz, Peter
, p. 19 - 29 (2019)
Ring closing metathesis (RCM) using Grubbs catalyst 2nd generation as a catalyst was applied to prepare series of novel unsaturated sultones with high yields. Many attempts, were applied for the cyclopropanation of the allylic sultones by Simmon-smith cyclopropanation using diethyl zinc/diiodomethane or Zn-Cu/diiodomethane but in each case the corresponding cyclic adduct was not formed. A novel palladium or preferably rhodium-catalyzed cyclopropanation of unsaturated sultones with ethyl diazoacetate was achieved by the transition metal-catalyzed transfer of a CH-CO2Et unit. The reaction was applied by a portion-wise addition of ethyl diazoacetate over 6h to a mixture of the sultones and palladium(II) acetate or rhodium(II) acetate dimer under low temperature (0-20 o C). The desired products of the cyclopropanation were achieved in each case, as a single diastereomer with 33- 37% yield in the allylic sultones and 10% for vinylic sultone.
3H-1,2-benzoxathiepine 2,2-dioxides: a new class of isoform-selective carbonic anhydrase inhibitors
Pustenko, Aleksandrs,Stepanovs, Dmitrijs,?alubovskis, Raivis,Vullo, Daniela,Kazaks, Andris,Leitans, Janis,Tars, Kaspars,Supuran, Claudiu T.
, p. 767 - 775 (2017)
A new chemotype with carbonic anhydrase (CA, EC 4.2.1.1) inhibitory action has been discovered, the homo-sulfocoumarins (3H-1,2-benzoxathiepine 2,2-dioxides) which have been designed considering the (sulfo)coumarins as lead molecules. An original synthetic strategy of a panel of such derivatives led to compounds with a unique inhibitory profile and very high selectivity for the inhibition of the tumour associated (CA IX/XII) over the cytosolic (CA I/II) isoforms. Although the CA inhibition mechanism with these new compounds is unknown for the moment, we hypothesize that it may be similar to that of the sulfocoumarins, i.e. hydrolysis to the corresponding sulfonic acids which thereafter anchor to the zinc-coordinated water molecule within the enzyme active site.
Preparation method of allylsulfonyl chloride
-
Paragraph 0017-0020, (2021/06/23)
The invention discloses a preparation method of allylsulfonyl chloride. The method comprises the following steps: simultaneously adding sodium allysulfonate, a catalyst, a polymerization inhibitor and an inert solvent into a reaction container, heating while stirring, dropwise adding thionyl chloride at the reaction temperature, and carrying out heat preservation reaction to obtain reaction liquid of allylsulfonyl chloride; and after the reaction is finished, filtering to obtain filtrate, and carrying out post-treatment on the filtrate to obtain the product allylsulfonyl chloride. According to the preparation method of the allylsulfonyl chloride, the prepared allylsulfonyl chloride has two reaction functional groups, namely a sulfonyl chloride group and an allyl double bond, so that the allylsulfonyl chloride serving as a raw material or an intermediate is better in selectivity and wider in application range. In the reaction process, a proper combined catalyst and a proper combined polymerization inhibitor are selected, so that the reaction activity is greatly improved, the stability of the product is ensured, the product polymerization is effectively prevented, and the reaction yield is improved.
Process for preparing 2 - (methylsulfonyl) - ethylene oxide and derivatives thereof
-
Paragraph 0038-0040; 0051-0053, (2021/09/29)
The invention relates to 2 - (methylsulfonyl) - ethylene oxide and a preparation method thereof, belonging to the technical field of synthesis of ethylene oxide derivatives, and the method comprises the following steps: raw materials are vinyl methyl sulfone or allyl methyl sulfone 1:2:4 or methylallyl sulfonic acid ester. @timetimepieces are added dropwise to m-chloroperoxybenzoic acid by dropwise adding time of 30 min, 25 min, 10 min, heating reflux 15 - 30h and cooling to room temperature filtration. When the starting material is a vinyl methyl sulfone, the product is 2 - (methylsulfonyl) - ethylene oxide. When the starting material is allyl methyl sulfone, the product is methyl -2 and 3 - propylene oxide sulfonate. When the starting material is methylallyl sulfonate, the product is methyl -2 and 3 - epoxypropane sulfonate. The molar ratio of the raw material and the m-chloroperbenzoic acid is 1: (1.8 - 2.4). The preparation method is simple and high in yield.
Aryl derivatives of 3H-1,2-benzoxathiepine 2,2-dioxide as carbonic anhydrase inhibitors
Pustenko, Aleksandrs,Nocentini, Alessio,Bala?ova, Anastasija,Alafeefy, Ahmed,Krasavin, Mikhail,?alubovskis, Raivis,Supuran, Claudiu T.
, p. 245 - 254 (2019/12/11)
A new series of homosulfocoumarins (3H-1,2-benzoxathiepine 2,2-dioxides) possessing various substitution patterns and moieties in the 7, 8 or 9 position of the heterocylic ring were prepared by original procedures and investigated for the inhibition of four physiologically relevant carbonic anhydrase (CA, EC 4.2.1.1) isoforms, the human (h) hCA I, II, IX and XII. The 8-substituted homosulfocoumarins were the most effective hCA IX/XII inhibitors followed by the 7-substituted derivatives, whereas the substitution pattern in position 9 led to less effective binders for the transmembrane, tumour-associated isoforms IX/XII. The cytosolic isoforms hCA I and II were not inhibited by these compounds, similar to the sulfocoumarins/coumarins investigated earlier. As hCA IX and XII are validated anti-tumour targets, with one sulphonamide (SLC-0111) in Phase Ib/II clinical trials, finding derivatives with better selectivity for inhibiting the tumour-associated isoforms over the cytosolic ones, as the homosulfocoumarins reported here, is of crucial importance.
Olefination with Sulfonyl Halides and Esters: E-Selective Synthesis of Alkenes from Semistabilized Carbanion Precursors
Górski, Bartosz,Basiak, Dariusz,Talko, Alicja,Basak, Tymoteusz,Mazurek, Tomasz,Barbasiewicz, Micha?
supporting information, p. 1774 - 1784 (2018/04/27)
Carbanions of sulfonyl halides and activated sulfonates add to carbonyl compounds, and so-formed aldol-type adducts spontaneously fragment into olefins. This transformation mimics the one-pot Julia olefination with (hetero)aryl sulfones, but the mechanism of fragmentation involves a four-membered intermediate, typical for reactivity of phosphorus reagents. Moreover, in contrast to the reactions of sulfones, sulfonates of fluorinated alcohols (TFE and HFI) produce byproducts that are easily removed during workup. In our report, we focus on reactions of unstabilized and semistabilized carbanion precursors: alkylsulfonates, and allyl- and benzylsulfonates, respectively. In particular for semistabilized systems, olefins were synthesized as predominant E isomers in good yields. The presented studies reveal that optimal reaction conditions, including the type of base and alcohol groups of the sulfonates, are different depending on stabilization of the carbanion precursors and structure of the carbonyl substrates. The practical synthetic guide is supplemented with a discussion of the mechanism, based on reactivity studies of intermediates and identification of side-products.
6-MEMBERED URACIL ISOSTERES
-
Paragraph 0780, (2018/06/12)
Provided herein are dUTPase inhibitors, compositions comprising such compounds and methods of using such compounds and compositions.
