- 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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- AEROBIC OXIDATIVE SYNTHESIS OF SULFONAMIDE USING Cu CATALYST
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The present invention relates to a method for oxidative synthesis of sulfonamides using copper catalysts. , Oxygen (O) is used. 2 The oxidative synthesis of sulfonamides (1) comprises reacting a 2 th or sulfonyl hydrazide primary amine with a sulfonyl hydrazide (sulfonamide) with a copper catalyst on a solvent under the conditions in which the sulphonamide is fed. The oxidation coupling of the present invention showed extensive substrate ranges in an amine comprising a 2 primary amine, 1 primary amine and amine hydrochloride salt. It is worth notable that non-reactive aliphatic sulfonyl hydrazides in previously reported anaerobic systems can be used for the aerobic oxidation coupling of the present invention. The oxidation coupling of the present invention has been more effective on large scale.
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Paragraph 0033-0037; 0039-0054; 0116-0117
(2021/04/06)
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- A Versatile Electrochemical Batch Reactor for Synthetic Organic and Inorganic Transformations and Analytical Electrochemistry
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A standardized and versatile electrochemical batch reactor that has wide applicability in both organic and inorganic synthesis and analytical electrochemistry has been developed. A variety of synthetic electrochemical transformations have been performed to showcase the versatility and demonstrate the reactor, including the synthesis of five Cu(I)-NHC complexes, two Au(I)-NHC complexes, and one Fe(II)-NHC complex as well as an Fe(III)-salen complex. The reactor is based on a commercially available vial with an adapted lid, making it inexpensive and highly flexible. It features a fixed interelectrode distance, which is crucial for reproducibility, along with the ability to accommodate a variety of interchangeable electrode materials. The reactor has also been used in conjunction with a parallel plate, allowing rapid screening and optimization of an organic electrochemical transformation. Cyclic voltammetry has been performed within the reactor on a range of imidazolium salt analytes with the use of an external potentiostat. The ability to use this reactor for both analytical and synthetic organic and inorganic chemistry is enabled by a flexible and characterizable design.
- Bourne, Richard A.,Kapur, Nikil,Nicholls, Thomas P.,Schotten, Christiane,Stephen, Hamish R.,Willans, Charlotte E.,Woodward, Madeleine
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p. 1084 - 1089
(2020/07/06)
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- Copper(II)-Photocatalyzed N-H Alkylation with Alkanes
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We report a practical method for the alkylation of N-H bonds with alkanes using a photoinduced copper(II) peroxide catalytic system. Upon light irradiation, the peroxide serves as a hydrogen atom transfer reagent to activate stable C(sp3)-H bonds for the reaction with a broad range of nitrogen nucleophiles. The method enables the chemoselective alkylation of amides and is utilized for the late-stage functionalization of N-H bond containing pharmaceuticals with good to excellent yields. The mechanism of the reaction was preliminarily investigated by radical trapping experiments and spectroscopic methods.
- Donabauer, Karsten,K?nig, Burkhard,Narobe, Rok,Yakubov, Shahboz,Zheng, Yi-Wen
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p. 8582 - 8589
(2020/09/23)
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- Iron-Catalyzed Hydroamination and Hydroetherification of Unactivated Alkenes
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The hydrofunctionalization of alkenes, explored for over 100 years, offers the potential for a direct, atom-economical approach to value-added products. While thermodynamically favored, the kinetic barrier to such processes necessitates the use of catalysts to control selectivity and reactivity. Modern variants typically rely on noble metals that require different ligands for each class of hydrofunctionalization, thereby limiting generality. This Letter describes a general iron-based system that catalyzes the hydroamination and hydroetherification of simple unactivated olefins.
- Marcyk, Paul T.,Cook, Silas P.
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supporting information
p. 1547 - 1550
(2019/03/08)
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- Multicomponent synthesis of sulfonamides from triarylbismuthines, nitro compounds and sodium metabisulfite in deep eutectic solvents
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A sustainable synthesis of sulfonamides using a copper-catalysed process starting from triarylbismuthines, Na2S2O5 and nitro compounds in a Deep Eutectic Solvent (DES) as a reaction medium is described. Thus, triarylbismuthines are used as reagents for the incorporation of SO2 into organic motifs. The bismuth salts formed as by-products can be easily removed from the crude reaction mixture by precipitation with water, while the use of volatile organic compounds (VOCs) as solvents can be avoided in the entire process. The eutectic mixture employed as the solvent is fully characterised, with the preliminary results proving its low toxicity. The designed DES also allows for a novel multicomponent reaction which saves time and reduces purification steps, energy and cost.
- Marset, Xavier,Torregrosa-Crespo, Javier,Martínez-Espinosa, Rosa M.,Guillena, Gabriela,Ramón, Diego J.
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supporting information
p. 4127 - 4132
(2019/08/07)
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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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- Hypervalent Iodine Mediated Sulfonamide Synthesis
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A new metal-free sulfonylation reaction is described. The method takes advantage of the Umpolung reactivity and group-transfer properties of iodine(III) compounds, combining hypervalent iodine reagents and sulfinate salts to deliver a clean and mild transfer of sulfonyl groups to amines and anilines. A total of 25 sulfonamides was synthesised in up to 99 % yield, even on gram-scale. The reaction mechanism was investigated by ESI-MS and DFT calculations.
- Poeira, Diogo L.,Macara, Jo?o,Faustino, Hélio,Coelho, Jaime A. S.,Gois, Pedro M. P.,Marques, M. Manuel B.
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supporting information
p. 2695 - 2701
(2019/04/08)
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- Cu-catalyzed aerobic oxidative synthesis of sulfonamides from sulfonyl hydrazides and amines
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An environmentally friendly route for sulfonamides has been developed. The oxidative coupling of sulfonyl hydrazides and amines was catalyzed by CuBr2 to produce various sulfonamides with the water and nitrogen gas as byproducts. Preliminary experiments revealed that the sulfonyl radical is likely to be involved in the reaction mechanism.
- Chung, Sohyun,Kim, Jinho
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supporting information
p. 792 - 795
(2019/02/16)
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- PTAB mediated open air synthesis of sulfonamides, thiosulfonates and symmetrical disulfanes
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A facile methodology has been described which has successfully simplified the generation of sulfonamides, thiosulfonates and symmetric disulfanes. This “trio” of reactions occur in an open air metal free atmosphere and has also been scaled up to grams making it suitable for commercialization. The reactions also have been successfully carried out with asymmetric variants, thus contributing to the chiral pool. The user friendly “trio” enables easy generation of these versatile sulfur analogues and the reaction condition employed depict an economic outline.
- Sarkar, Debayan,Ghosh, Manoj Kumar,Rout, Nilendri
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supporting information
p. 2360 - 2364
(2018/05/24)
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- Copper-Catalyzed Oxidative Dehydrogenative C(sp3)?H Bond Amination of (Cyclo)Alkanes using NH-Heterocycles as Amine Sources
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A copper-catalyzed oxidative C(sp3)?H/N?H coupling of NH-heterocycles with affordable (cyclo)alkanes has been developed. This procedure involves C(sp3)?N bond formation through a radical pathway generated by homolytic cleavage of di-tert-butyl peroxide and trapping of the radical(s) by copper catalysts. The reaction tolerates a series of functional groups, such as bromo, fluoro, ester, ketone, nitrile, methyl, and methoxy. free-NH-containing indoles, pyrroles, pyrazoles, indazoles, and benzotriazoles are successfully N-alkylated.
- Wang, Chang-Sheng,Wu, Xiao-Feng,Dixneuf, Pierre H.,Soulé, Jean-Fran?ois
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p. 3075 - 3082
(2017/08/18)
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- Amidation via ligand-free direct oxidative C(sp3)-H/N[sbnd]H coupling with Cu-CPO-27 metal-organic framework as a recyclable heterogeneous catalyst
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A copper-based metal-organic framework Cu-CPO-27 was synthesized, and used as a recyclable catalyst for the amidation of unactivated alkanes by benzamides via direct oxidative C(sp3)-H/N[sbnd]H coupling under ligand-free conditions. Using a catalytic amount of the Cu-CPO-27 for the transformation, high yields of N-cyclohexyl benzamides were achieved. The Cu-CPO-27 was more catalytically active than other Cu-MOFs such as Cu3(BTC)2, Cu(BDC), Cu(EDB), Cu2(BPDC)2(BPY), Cu2(BDC)2(DABCO), and Cu2(EDB)2(BPY). The Cu-CPO-27 also exhibited advantages as compared to several copper-based salts, including Cu(OAc)2, CuCl2, CuBr, CuI, CuCl, Cu(NO3)2, and CuSO4. The Cu-CPO-27 catalyst could be reused several times for the amidation transformation while its catalytic activity was not decreased significantly. To the best of our knowledge, the amidation of unactivated alkanes by benzamides via direct oxidative C(sp3)-H/N[sbnd]H coupling was not previously performed under heterogeneous catalysis conditions.
- Hoang, Thanh T.,Nguyen, Hanh T.H.,Le, Tien T.,Le, Dung T.,Truong, Thanh,Phan, Nam T.S.
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p. 8241 - 8251
(2016/11/23)
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- On the understanding of BF3·Et2O-promoted intra- and intermolecular amination and oxygenation of unfunctionalized olefins
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BF3·Et2O was found to be effective for both intra- and intermolecular amination and oxygenation of unfunctionalized olefins. In the presence of 3 equiv. of BF3·Et2O, intramolecular hydroamination of N-(pent-4-enyl)-p-toluenesulfonamides, N-(hex-5-enyl)-p-toluenesulfonamides, intermolecular hydroamination between sulfonamides and cyclohexene, norbornene or styrene, lactonization of pent-4-enoic acid or hex-5-enoic acid compounds and esterification of cyclohexene with different carboxylic acids all proceeded readily, leading to the corresponding amination or oxygenation products in up to 99% isolated yields. Preliminary NMR experiments and DFT calculations suggested that the intramolecular hydroamination reactions proceeded via a sulfonimidic acid intermediate (N=S-OH), and formation of the corresponding Bronsted acid HF or HBF4 was less likely.
- Yang, Chun-Hua,Fan, Wen-Wen,Liu, Gong-Qing,Duan, Lili,Li, Lin,Li, Yue-Ming
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p. 61081 - 61093
(2015/08/03)
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- A One-Pot, fast, and efficient amidation of carboxylic acids, α-amino acids and sulfonic acids using pph3/n-chlorobenzotriazole system
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Triphenylphosphine (PPh3)/N-chlorobenzotriazole (NCBT), and amine (primary and secondary aliphatic amines and also substituted anilines) in CH2Cl2 efficiently converted carboxylic acids, α-amino acids, and sulfonic acids to the corresponding amides and sulfonamides at room temperature. Good to excellent yields, inexpensive, and fast reaction conditions are the important features of this procedure.
- Rouhi-Saadabad, Hamed,Akhlaghinia, Batool
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p. 1703 - 1714
(2015/09/15)
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- Metal-free direct construction of sulfonamides via iodine- mediated coupling reaction of sodium sulfinates and amines at room temperature
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A simple, practical, and metal-free protocol has been developed for the synthesis of sulfonamides from sodium sulfinates and various amines through an iodine-mediated SN bond formation reaction at room temperature. This green reaction is cost-effective, operationally straightforward, and especially proceeds under very mild conditions to afford the target products in good to excellent yields (up to 98%).
- Wei, Wei,Liu, Chunli,Yang, Daoshan,Wen, Jiangwei,You, Jinmao,Wang, Hua
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supporting information
p. 987 - 992
(2015/03/30)
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- Oxidative debenzylation of N-benzyl amides and O-benzyl ethers using alkali metal bromide
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The oxidative debenzylation of N-benzyl amides and O-benzyl ethers was promoted with high efficiency by a bromo radical formed through the oxidation of bromide from alkali metal bromide under mild conditions. This reaction provided the corresponding amides from N-benzyl amides and carbonyl compounds from O-benzyl ethers in high yields.
- Moriyama, Katsuhiko,Nakamura, Yu,Togo, Hideo
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supporting information
p. 3812 - 3815
(2014/08/05)
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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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- 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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- The hydroamination of alkenes with sulfonamides catalyzed by the recyclable silica gel supported triflic acid
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The vast applications of triflic acid (TfOH) in catalysis are severely limited by its corrosive and fuming properties. Immobilization of TfOH on silica gel well solves these problems and affords efficient recovery and reusability of TfOH. Two types of supported TfOH, the prepared silica gel supported TfOH and the in situ silica gel adsorbed TfOH, both exhibit good catalytic activity and reusability in the hydroamination of alkene with sulfonamide. The in situ silica gel adsorbed catalyst has been used for 5 runs with maintained reactivities and yields, which are superior to the performance of the prepared silica gel supported TfOH. For a series of alkenes and various sulfonamides, the heterogeneous hydroamination reactions catalyzed by both types of silica gel supported TfOH to afford similar moderate to excellent yields.
- Liu, Pei Nian,Xia, Fei,Zhao, Zheng Le,Wang, Qing Wei,Ren, Yu Jie
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supporting information; experimental part
p. 6113 - 6117
(2011/12/01)
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- Sulfonamide synthesis using N-hydroxybenzotriazole sulfonate: An alternative to pentafluorophenyl (PFP) and trichlorophenyl (TCP) esters of sulfonic acids
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The N-hydroxybenzotriazole (HOBt) sulfonate esters undergo amidation under ambient conditions in the presence of di-isopropylethyl amine. This method can be applied to varieties of amines including sterically hindered amino acid esters in less time with reasonably good yields. HOBt ester of sulfonic acids can be a replacement for pentafluorophenyl and trichlorophenyl ester as well as chloride moiety of sulfonyl chloride for amidation.
- Palakurthy, Nani Babu,Mandal, Bhubaneswar
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p. 7132 - 7134
(2012/02/01)
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- Highly efficient and reusable ionic liquids for the catalyzed hydroamination of alkenes with sulfonamides, carbamates, and carboxamides
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SO3H-Functionalized ionic liquids were found to be efficient and reusable catalysts in the hydroamination of sulfonamides, carboxamides, p-nitroaniline and carbamates with nonactivated alkenes. The hydroamination could be performed on a large scale and the acidic ionic liquid catalyst could be reused successfully. Georg Thieme Verlag Stuttgart.
- Yang, Lei,Xu, Li-Wen,Xia, Chun-Gu
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experimental part
p. 1969 - 1974
(2009/12/26)
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- Mild and general method for the synthesis of sulfonamides
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Reaction of methyl sulfinates with lithium amides followed by 3-chloroperoxybenzoic acid oxidation of the resulting sulfinamides provides primary, secondary, and tertiary alkane-, arene-and heteroarenesulfonamides in high yields. This constitutes a mild and facile experimental protocol that avoids the use of hazardous, unstable, or volatile reagents and does not affect the configurational stability of the amines. Georg Thieme Verlag Stuttgart.
- Garcia Ruano, Jose Luis,Parra, Alejandro,Yuste, Francisco,Mastranzo, Virginia M.
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p. 311 - 319
(2008/12/22)
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- Heteropoly acids: a green and efficient heterogeneous Br?nsted acidic catalyst for the intermolecular hydroamination of olefins
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Intermolecular hydroamination of non-activated olefins with amides and benzyl carbamate proceeds efficiently in the presence of environmentally benign silicotungstic acid (HSiW) catalyst under mild conditions in air to afford addition products in good to excellent yields.
- Yang, Lei,Xu, Li-Wen,Xia, Chun-Gu
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p. 2882 - 2885
(2008/09/21)
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- A practical and efficient method for the preparation of sulfonamides utilizing Cl3CCN/PPh3
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Cl3CCN in combination with PPh3 proved to be a highly reactive reagent for the conversion of sulfonic acids to the corresponding sulfonyl chlorides in refluxing CH2Cl2. Upon reaction with amines, the corresponding sulfonamides were obtained in good to excellent yields.
- Chantarasriwong, Oraphin,Jang, Doo Ok,Chavasiri, Warinthorn
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p. 7489 - 7492
(2007/10/03)
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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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- ROMP-generated oligomeric sulfonyl chlorides as versatile soluble scavenging agents.
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[reaction: see text] A new method for homogeneous nucleophilic scavenging employing oligomeric sulfonyl chloride (OSC) reagents is described. The method utilizes OSC to rapidly scavenge a variety of amines that are present in excess. The OSC reagents are generated from ROM polymerization of 2-chlorosulfonyl-5-norbornene utilizing the second generation Grubbs catalyst to produce oligomers of varying size as stable, free-flowing powders. Following the scavenging event, these oligomers are precipitated with ethyl acetate leaving products in excellent yield and purity.
- Moore, Joel D,Herpel, Russell H,Lichtsinn, Joy R,Flynn, Daniel L,Hanson, Paul R
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p. 105 - 107
(2007/10/03)
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- Arenesulfonylheterocycles (I): Synthesis and reactions of 2-benzenesulfonyl-4,5-dichloropyridazin-3-ones with amines
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The direct sulfonylation of 4,5-dichloropyridazin-3-ones with some benzenesulfonyl chlorides in the presence of base in tetrahydrofuran gave only the corresponding N-sulfonylated product. The reaction of 2-benzenesulfonyl-4,5-dichloropyridazin-3-ones with some aliphatic amines under neutral conditions afforded 5-alkylamino-2-benzenesulfonyl-4-chloropyridazin-3-ones and/or the corresponding N-alkyl-benzenesulfonamides.
- Kweon, Deok-Heon,Kim, Ho-Kyun,Kim, Jeum-Jong,Chung, Hyun A.,Woo, Song Lee,Kim, Sung-Kyu,Yoon, Yong-Jin
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p. 203 - 211
(2007/10/03)
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