- Phosphine/Photoredox Catalyzed Anti-Markovnikov Hydroamination of Olefins with Primary Sulfonamides via α-Scission from Phosphoranyl Radicals
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New strategies to access radicals from common feedstock chemicals hold the potential to broadly impact synthetic chemistry. We report a dual phosphine and photoredox catalytic system that enables direct formation of sulfonamidyl radicals from primary sulf
- Chinn, Alex J.,Sedillo, Kassandra,Doyle, Abigail G.
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supporting information
p. 18331 - 18338
(2021/11/10)
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- Sulfonamide Synthesis through Electrochemical Oxidative Coupling of Amines and Thiols
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Sulfonamides are key motifs in pharmaceuticals and agrochemicals, spurring the continuous development of novel and efficient synthetic methods to access these functional groups. Herein, we report an environmentally benign electrochemical method which enables the oxidative coupling between thiols and amines, two readily available and inexpensive commodity chemicals. The transformation is completely driven by electricity, does not require any sacrificial reagent or additional catalysts and can be carried out in only 5 min. Hydrogen is formed as a benign byproduct at the counter electrode. Owing to the mild reaction conditions, the reaction displays a broad substrate scope and functional group compatibility.
- Laudadio, Gabriele,Barmpoutsis, Efstathios,Schotten, Christiane,Struik, Lisa,Govaerts, Sebastian,Browne, Duncan L.,No?l, Timothy
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supporting information
(2019/04/16)
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- Sulfonamide Synthesis through Electrochemical Oxidative Coupling of Amines and Thiols
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Sulfonamides are key motifs in pharmaceuticals and agrochemicals, spurring the continuous development of novel and efficient synthetic methods to access these functional groups. Herein, we report an environmentally benign electrochemical method which enables the oxidative coupling between thiols and amines, two readily available and inexpensive commodity chemicals. The transformation is completely driven by electricity, does not require any sacrificial reagent or additional catalysts and can be carried out in only 5 min. Hydrogen is formed as a benign byproduct at the counter electrode. Owing to the mild reaction conditions, the reaction displays a broad substrate scope and functional group compatibility.
- Laudadio, Gabriele,Barmpoutsis, Efstathios,Schotten, Christiane,Struik, Lisa,Govaerts, Sebastian,Browne, Duncan L.,No?l, Timothy
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supporting information
p. 5664 - 5668
(2019/04/17)
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- 1,3,4-OXADIAZOLE SULFONAMIDE DERIVATIVE COMPOUNDS AS HISTONE DEACETYLASE 6 INHIBITOR, AND THE PHARMACEUTICAL COMPOSITION COMPRISING THE SAME
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The present invention relates to novel compounds represented by the formula I having histone deacetylase 6 (HDAC6) inhibitory activity, stereoisomers thereof or pharmaceutically acceptable salts thereof, the use thereof for the preparation of therapeutic medicaments, pharmaceutical compositions containing the same, a method for treating diseases using the composition, and methods for preparing the novel compounds. (I) The novel compounds, stereoisomers thereof or pharmaceutically acceptable salts thereof according to the present invention have histone deacetylase (HDAC) inhibitory activity and are effective for the prevention or treatment of HDAC6-mediated diseases.
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Paragraph 1243; 1244; 1245
(2017/02/24)
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- Carbazole-containing sulfonamides and sulfamides: Discovery of cryptochrome modulators as antidiabetic agents
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A series of novel carbazole-containing sulfonamides and sulfamides were synthesized. A structure-activity relationship study of these compounds led to the identification of potent cryptochrome modulators. Based on the results of efficacy studies in diet-induced obese (DIO) mice, and the desired pharmacokinetic parameters, compound 41 was selected for further profiling.
- Humphries, Paul S.,Bersot, Ross,Kincaid, John,Mabery, Eric,McCluskie, Kerryn,Park, Timothy,Renner, Travis,Riegler, Erin,Steinfeld, Tod,Turtle, Eric D.,Wei, Zhi-Liang,Willis, Erik
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p. 757 - 760
(2016/05/24)
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- Palladium-Catalyzed cascade sp2 c?H bond functionalizations allowing one-Pot access to 4?Aryl-1,2,3,4-tetrahydroquinolines from n?Allyl?N?arylsulfonamides
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We have developed a palladium-catalyzed cascade reaction allowing an efficient synthesis of 4-aryl-1,2,3,4-tetrahydroquinolines from N-allyl-N-arylsulfonamides and benzenesulfonyl chlorides. In this transformation, two C(sp2)?C(sp3) bonds were formed via activation of C(sp2)?H bonds. The reaction proceeds using the easily accessible catalyst PdCl2, with Li2CO3 as inexpensive base and CuBr as additive, and tolerates a wide variety of substituents on both reaction partners.
- Yuan, Kedong,Soule, Jean-Francois,Dorcet, Vincent,Doucet, Henri
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p. 8121 - 8126
(2018/05/23)
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- Metal-free reductive cleavage of C-N and S-N bonds by photoactivated electron transfer from a neutral organic donor
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A photoactivated neutral organic super electron donor cleaves challenging arenesulfonamides derived from dialkylamines at room temperature. It also cleaves a)ArC-NR and b)ArN-C bonds. This study also highlights the assistance given to these cleavage reactions by the groups attached to N in (a) and to C in (b), by lowering LUMO energies and by stabilizing the products of fragmentation. Radical fragmentations: Electron transfer from the photoactivated neutral electron donor 1 delivers high yields of S-N and C-N cleavage products for a range of nitrogen-containing species. These reactions proceed at room temperature and under mild reaction conditions in the absence of any metal reagents. DMF=N,N-dimethylformamide, Ts=4-toluenesulfonyl.
- O'Sullivan, Steven,Doni, Eswararao,Tuttle, Tell,Murphy, John A.
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supporting information
p. 474 - 478
(2014/01/23)
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- Transition metal-free intermolecular a-C-H amination of ethers at room temperature
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We describe a new method for the intermolecular amination of the α-C-H bonds of ethers. A hypervalent iodine reagent was used as oxidant to enable the amination of cyclic and acyclic alkyl ethers with a wide range of amides, imides, and amines. The amination occurred at room temperature and without a transition metal catalyst. The method could be used to synthesize the anti-cancer prodrug Tegafur and its analogues.
- Buslov, Ivan,Hu, Xile
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supporting information
p. 3325 - 3330
(2015/02/02)
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- Stereoselective direct reductive amination of ketones with electron-deficient amines using Re2O7/NaPF6 catalyst
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The first example of direct reductive amination (DRA) of ketones with electron-deficient amines (EDA) such as Cbz-, Boc-, EtOCO-, Fmoc-, Bz-, ArSO2-, etc. protected amines have been achieved using catalytic Re2O7/NaPF6. Excellent chemoselectivities as well as diastereoselectivity (for 2-alkyl cyclohexanones) were obtained. The Royal Society of Chemistry 2013.
- Das, Braja Gopal,Ghorai, Prasanta
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supporting information
p. 4379 - 4382
(2013/08/23)
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- Convenient synthesis of primary sulfonamides
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An efficient protocol for a one-pot synthesis of mono-sulfonamides has been developed. It features utilization of excess of sulfonylating agent followed by base mediated recovery of the primary sulfonamide.
- Greenfield, Alexander,Grosanu, Cristina
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body text
p. 6300 - 6303
(2009/04/06)
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- Photochemistry of N-acetyl-, N-trifluoroacetyl-, N- mesyl-, and N-tosyldibenzothiophene sulfilimines
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(Chemical Equation Presented) Time-resolved infrared (TRIR) spectroscopy, product studies, and computational methods were applied to the photolysis of sulfilimines derived from dibenzothiophene that were expected to release acetylnitrene, trifluoroacetylnitrene, mesylnitrene, and tosylnitrene. All three methods provided results for acetylnitrene consistent with literature precedent and analogous experiments with the benzoylnitrene precursor, i.e., that the ground-state multiplicity is singlet. In contrast, product studies clearly indicate triplet reactivity for trifluoroacetylnitrene, though TRIR experiments were more ambiguous. Product studies suggest that these sulfilimines are superior sources for sulfonylnitrenes, which have triplet grounds states, to the corresponding azides, and computational studies shed light on the electronic structure of the nitrenes.
- Desikan, Vasumathi,Liu, Yonglin,Toscano, John P.,Jenks, William S.
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p. 4398 - 4414
(2008/09/21)
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- InBr3 Catalyzed intermolecular hydroamination of unactivated alkenes
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InBr3 has been demonstrated to be a simple catalyst for the intermolecular hydroamination of unactivated alkenes to produce tosyl- and mesyl-protected amines in moderate to good yields.
- Huang, Jing-Mei,Wong, Chek-Ming,Xu, Feng-Xia,Loh, Teck-Peng
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p. 3375 - 3377
(2008/02/12)
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- Platinum-based catalysts for the hydroamination of olefins with sulfonamides and weakly basic anilines
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Electrophilic Pt(II) complexes catalyze efficient hydroaminations of olefins by sulfonamides and weakly basic anilines. Catalysts include the structurally characterized complex (COD)Pt(OTf)2 (1) and the known dimer [PtCl2(C2H4)]2, activated by AgBF4. Experiments with substituted anilines establish an empirical pKa cutoff (conjugate acid pKa a ≈ = -6) with various para substituents hydroaminate olefins such as cyclohexene in yields greater than 95% at 90 °C. Hydroamination of propylene by p-toluenesulfonamide proceeds with Markovnikov selectivity, suggesting a mechanism that involves olefin activation at Pt. With norbornene and p-toluenesulfonamide as the substrates and 1 as the catalyst, intermediate [(COD)Pt-(norbornene)2][OTf]2 (3) was identified and characterized by 19F and 195Pt NMR spectroscopies and mass spectrometry. Kinetic studies provide the empirical rate law, rate = kobs[Pt][sulfonamide], and are consistent with a mechanism in which attack of a sulfonamide on the Pt-coordinated olefin is the rate-determining step.
- Karshtedt, Dmitry,Bell, Alexis T.,Tilley, T. Don
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p. 12640 - 12646
(2007/10/03)
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- Oxidative deamination of various primary amines to the corresponding carbonyl compounds by using N-tert-butylphenylsulfinimidoyl chloride
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Various linear and non-linear primary amines were oxidatively deaminated to afford the corresponding carbonyl compounds in good to excellent yields by the following procedure: (i) initial formation of their N-cyclohexylated or N-mesylated derivatives, (ii) subsequent oxidation of these derivatives by using N-tert-butylphenylsulfinimidoyl chloride (1) and DBU, (iii) one-pot acid-hydrolysis of thus formed imines to carbonyl compounds.
- Matsuo, Jun-Ichi,Kawana, Asahi,Fukuda, Yoshio,Mukaiyama, Teruaki
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p. 712 - 713
(2007/10/03)
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- A convenient synthesis of N-alkyl-(E)-1-alkenesulfonamides
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A series of vinylsulfonamides 3 has been synthesised through a condensation of N-Boc-methanesulfonamides 1 and aldehydes 2. O-Boc-2-hydroxyalkanesulfonamides were identified as intermediates, arising from N-O transfer of the Boc group. Elimination of OBoc gave the vinylsulfonamides.
- Tozer, Matthew J.,Woolford, Alison J. A.,Linney, Ian D.
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p. 186 - 188
(2007/10/03)
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- Reductive deprotection of allyl, benzyl and sulfonyl substituted alcohols, amines and amides using a naphthalene-catalysed lithiation
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The reaction of different protected alcohols, amines and amides with lithium and a catalytic amount of naphthalene (4 mol %) in THF at low temperature leads to their deprotection under very mild reaction conditions, the process being in many cases chemoselective.
- Alonso, Emma,Ramon, Diego J.,Yus, Miguel
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p. 14355 - 14368
(2007/10/03)
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- 1,3,2λ5-Benzothiazaphosphole 2-Oxide and 1,3,2λ5-Benzoxazaphosphole 2-Oxide Derivatives, New and Versatile Phosphorylating Reagents
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The synthesis of the highly reactive five-membered cyclic phosphorylating reagents 6a and 12 is decribed.The reagent 6a monophosphorylates alcohols without ring opening, whereas 12 diphosphorylates with ring opening yielding phosphate triesters.
- Jacob, Peter,Richter, Wolfgang,Ugi, Ivar
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p. 519 - 522
(2007/10/02)
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- The Reduction of Tertiary N-Stryrylsulphonamides and Other Tertiary Sulphonamides by Magnesium and Methanol.
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The preparation of three N-substituted-N-2-phenylethenylsulphonamides is described.On reduction with magnesium and methanol N-phenyl-N-2-phenylethenyltoluene-p-sulphonamide gives cleanly N-phenyl-N-2-phenylethylamine, N-phenyl-N-2-phenylethenylmethanesulphonamide gives some N-phenyl-N-2-phenylethylamine, but also N-phenyl-N-2-phenylethylmethanesulphonamide and N-phenylmethanesulphonamide, and N-cyclohexyl-N-2-phenylethenylmethanesulphonamide gives N-cyclohexyl-N-2-phenylethylmethanesulphonamide and N-cyclohexylmethanesulphonamide.The nitrogen-sulphur bond in N-methyl-N-phenyltoluene-p-sulphonamide and in N-toluene-p-sulphonylpiperidine is also reductively cleaved by magnesium and methanol, but not that in N-methyl-N-phenylmethanesulphonamide.
- Brettle, Roger,Hilton, Neville A.,Shibib, Sa'ad M.
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p. 3712 - 3720
(2007/10/02)
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- α,N-Alkanesulfonamide Dianions: Formation and Chemoselective C-Alkylation
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Mono-N-substituted alkanesulfonamides such as 11 (Scheme I) can be treated with 2 equiv of a strong base (n-butyllithium or LDA) to generate the hitherto unreported dianionic species 12.Addition of electrophiles (alkylhalides, aldehydes, ketones, nitriles) to THF solutions of these dianions results in clean, chemoselective reaction on the carbon atom.Removal of the "protecting" group from nitrogen releases a primary sulfonamide, which may then be selectively functionalized.This method permits the preparation of a wide variety of substituted sulfonamides that might otherwise prove difficult to synthesize.As demonstration of the further utility of these adducts, β-hydroxy sulfonamides such as 14 were converted to either β-styrenesulfonamides 15 (and 16) or 1,2-thiazetidine 1,1-dioxides (18) (Scheme II).
- Thompson, Mark E.
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p. 1700 - 1703
(2007/10/02)
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