- Rare-Earth-Catalyzed Transsulfinamidation of Sulfinamides with Amines
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A rare-earth-catalyzed transsulfinamidation of primary sulfinamides with alkyl, aryl, and heterocyclic amines for the synthesis of diverse secondary and tertiary sulfinamides has been realized. Unlike transition metal-catalyzed cross-coupling approaches restricted to non-commercially available disubstituted O-benzoyl hydroxylamines, this newly developed protocol is suitable for diverse readily available primary and secondary amines without any modifications. Excellent catalytic activity and selectivity are achieved with Eu(OTf)3 under mild reaction conditions, which extends the applicability of rare-earth catalysis.
- Tu, Tao,Wang, Chaoyu,Wen, Daheng,Zheng, Qingshu
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supporting information
p. 3718 - 3723
(2021/05/31)
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- Ni/NHC-catalyzed cross-coupling of methyl sulfinates and amines for direct access to sulfinamides
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It was reported to develop a simple and convenient method for the Ni/NHC-catalyzed cross-coupling of methyl sulfinates and amines without an acid/base to afford secondary or tertiary sulfinamides in moderate to good yields. The method can provide the desired products with broad substrate scope, good chemoselectivity and good functional group compatibility. The presented approach may enrich the Ni/NHC catalyst system and promote the applications of methyl sulfinates in the organic sulfur chemistry.
- Li, Gang-Jian,Pan, You-Lu,Liu, Yan-Ling,Xu, Hai-Feng,Chen, Jian-Zhong
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supporting information
(2019/10/28)
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- Efficient Synthesis of Sulfinate Esters and Sulfinamides via Activated Esters of p -Toluenesulfinic Acid
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Sulfinate esters were prepared by the process of activating p -toluenesulfinic acid with either cyanuric chloride, methanesulfonyl chloride, or 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC-HCl). Activation of p -toluenesulfinic acid with cyanuric chloride led to the formation of sulfinate esters that were accompanied by the formation of the corresponding sulfones. The use of methanesulfonyl chloride for activation via methanesulfonic p -toluenesulfinic anhydride afforded mixtures of sulfinate esters and methanesulfonates. The use of the carbodiimide EDC proved to yield the best results with the highly selective formation of the target sulfinate esters. The use of trimethylacetic p -toluenesulfinic anhydride or cyanuric chloride to achieve the synthesis of sulfinamides proved to be ineffective due to poor chemoselectivity of the nucleophilic attack on the activated p -toluenesulfinic acid anhydride. Ultimately, the use of EDC-HCl to form the sulfinamides proved to be the best pathway for synthesis.
- Gafur, Sayed Habibul,Waggoner, Stephanie L.,Jacobsen, Eric,Hamaker, Christopher G.,Hitchcock, Shawn R.
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p. 4855 - 4866
(2018/12/13)
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- Copper-Catalyzed Transsulfinamidation of Sulfinamides as a Key Step in the Preparation of Sulfonamides and Sulfonimidamides
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Secondary or tertiary sulfinamides are prepared by copper-catalyzed transsulfinamidation of primary sulfinamides with O-benzoyl hydroxylamines. Subsequent oxidations of the resulting products lead to the corresponding sulfonamides. Treatment of N-aryl sulfinamides with O-benzoyl hydroxylamines under copper catalysis provides N-aryl sulfonimidamides.
- Yu, Hao,Li, Zhen,Bolm, Carsten
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supporting information
p. 15602 - 15605
(2018/11/10)
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- A New, Practical One-Pot Synthesis of Unprotected Sulfonimidamides by Transfer of Electrophilic NH to Sulfinamides
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Unprotected tertiary sulfonimidamides have been prepared in good to excellent yields in a one-pot transformation from tertiary sulfinamides through NH transfer. The reaction is mediated by commercially available (diacetoxyiodo)benzene and ammonium carbamate in methanol under convenient conditions. A wide range of functional groups are tolerated and initial results indicate that the NH transfer is stereospecific. A small molecule X-ray analysis of NH sulfonimidamide 2 a and its behavior in selected in vitro assays in comparison to the matched sulfonamide are also reported. This new reaction provides a safe, short and efficient approach to sulfonimidamides, which have been the subject of recent, growing interest in the life sciences.
- Izzo, Flavia,Sch?fer, Martina,Stockman, Robert,Lücking, Ulrich
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supporting information
p. 15189 - 15193
(2017/10/12)
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- Copper-Catalyzed Oxidative Synthesis of Sulfinamides Using Thiols or Disulfides with Amines
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Copper-catalyzed coupling of thiols with amines was used to synthesize numerous sulfinamides in excellent yields. Sulfenamides or sulfonamides were also formed as reaction byproducts albeit in trace quantities. The procedure is carried out as a one step a
- Taniguchi, Nobukazu
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p. 2157 - 2162
(2016/05/09)
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- Functionalization of mesoporous carbon with superbasic MgO nanoparticles for the efficient synthesis of sulfinamides
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Highly basic MgO nanoparticles with different sizes have been successfully immobilized over mesoporous carbon with different pore diameters by a simple wet-impregnation method. The prepared catalysts have been characterized by various sophisticated techniques, such as XRD, nitrogen adsorption, electron energy loss spectroscopy, high-resolution TEM, X-ray photoelectron spectroscopy, and the temperature-programmed desorption of CO2. XRD results reveal that the mesostructure of the support is retained even after the huge loading of MgO nanoparticles inside the mesochannels of the support. It is also demonstrated that the particle size and dispersion of the MgO nanoparticles on the support can be finely controlled by the simple adjustment of the textural parameters of the supports. Among the support materials studied, mesoporous carbon with the largest pore diameter and large pore volume offered highly crystalline small-size cubic-phase MgO nanoparticles with a high dispersion. The basicity of the MgO-supported mesoporous carbons can also be controlled by simply changing the loading of the MgO and the pore diameter of the support. These materials have been employed as heterogeneous catalysts for the first time in the selective synthesis of sulfinamides. Among the catalysts investigated, the support with the large pore diameter and high loading of MgO showed the highest activity with an excellent yield of sulfinamides. The catalyst also showed much higher activity than the pristine MgO nanoparticles. The effects of the reaction parameters, including the solvents and reaction temperature, and textural parameters of the supports in the activity of the catalyst have also been demonstrated. Most importantly, the catalyst was found to be highly stable, showing excellent activity even after the third cycle of reaction. Reuse and recycle: Highly basic MgO-functionalized mesoporous carbon with different pore diameters has been prepared (see picture). The material showed a much higher performance in the synthesis of sulfinamides than pure MgO nanoparticles. The catalyst was also highly stable and could be reused several times without affecting its activity. Copyright
- Chakravarti, Rajashree,Mano, Ajayan,Iwai, Hideo,Aldeyab, Salem S.,Kumar, R. Pradeep,Kantam, M. Lakshmi,Vinu, Ajayan
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supporting information; experimental part
p. 6673 - 6682
(2011/08/05)
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- p-Tolylsulfinyl Amides: Reagents for Facile Electrophilic Functionalization of Olefins
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A variety of olefins were found to react with sulfinyl amides in the presence of POCl3 to give β-chlorosulfides and β-hydroxysulfides in good yields. In the absence of nucleophiles, p-tolylsulfinyl amides were found to react with olefins with the formation of allylsulfoxides.
- Krasnova, Larissa B.,Yudin, Andrei K.
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p. 2584 - 2587
(2007/10/03)
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- Electrochemical oxidation of N-p-toluenesulfinamides
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Matrix presented Contrasting and interesting electrochemical behavior is observed in anodic oxidation of N-substituted p-toluenesulfinamides under controlled current conditions. For sulfinamides derived from secondary alkylamines and primary arylamines, the N-sulfinyl group is removed and the corresponding amines are formed; for sulfinamides derived from primary alkylamines, sulfur oxidation yields the corresponding sulfonamides in good yields.
- D'Oca, Marcelo G. Montes,Russowsky, Dennis,Canto, Karen,Gressler, Tanara,Goncalves, Reinaldo S.
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p. 1763 - 1766
(2007/10/03)
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- THERMOLYSES AND REACTIONS WITH NUCLEOPHILES OF N-SULFUR-GROUP-SUBSTITUTED SULFOXIMINES
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Thermolyses and reactions with nucleophiles of S,S-diphenylsulfoximines (1) bearing the following N-sulfur-substituents, i.e., N-p-tolylthio-(b), N-p-tolylsulfinyl-(c), N-(N'-p-tolylsulfonyl-p-toluenesulfinimidoyl)-(d), N-(S',S'-diphenylsulfonio)-(e), N-p-tolylsulfonyl-(f), and N-(N'-p-tolylsulfonyl-p-toluenesulfonimidoyl)-(g), have been examined.The former three sulfoximines (1b-d) are thermally unstable and readily decompose to form diphenyl sulfoxide and diphenyl sulfide by the initial cleavage of the S-N linkage in the original sulfoximines.The latter three sulfoximines (1e-g) fairly stable thermally. 1b-d were found to react with several nucleophiles to afford the corresponding sulfenylated, sulfinylated or sulfinimidoylated products together with N-unsubstituted sulfoximine(1a). 1e was found to react with potassium hydroxide/methanol or chloramine-T/N,N-dimethylformamide to afford diphenyl sulfoxide or S,S-diphenyl-(N-p-tolylsulphonyl)sulfilimine along with 1a in good yields.The latter two sulfoximines (1f,g) were found to be inert in the treatment with a few nucleophiles.S,S-Diphenyl-(N-p-tolylthio)-(1b), -(N-p-tolylsulfinyl)-(1c), -(N-p-toluenesulfinimidoyl)-(1d), and -N-(diphenylsulfonio)-(1e) sulfoximines are all new to sulfoximine chemistry and their chemical behavior and reactivity have not been explored.As a preliminary step, thermal decompositions and reactions of these sulfoximines with several nucleophiles have been examined.
- Oae, Shigeru,Akutagawa, Kunihiko,Furukawa, Naomichi
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p. 223 - 234
(2007/10/02)
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- Novel One-Step Preparation of Sulfinic Acid Derivatives from Sulfinic Acid
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Convenient one-step syntheses of sulfinamides and sulfinate esters from sulfinic acids were achieved by using coupling reagents, such as 2-chloro-1-methylpyridinium iodide, γ-saccharine chloride, N,N'-dicyclohexylcarbodiimide, and diethyl azodicarboxylate and triphenylphosphine.Ammonolysis of sulfinate esters also give sulfinamides.Keyword- sulfinic acid; sulfinamide; sulfinate ester; sulfinyl-transfer reagent; coupling reaction; 2-chloro-1-methylpyridinium iodide; γ-saccharine chloride; N,N'-dicyclohexylcarbodiimide; diethyl azodicarboxylate; triphenylphosphine
- Furukawa, Mitsuru,Ohkawara, Tadashi,Noguchi, Yoshihide,Nishikawa, Masumi,Tomimatsu, Masahide
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p. 134 - 141
(2007/10/02)
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