- Nanosized CdS as a Reusable Photocatalyst: The Study of Different Reaction Pathways between Tertiary Amines and Aryl Sulfonyl Chlorides through Visible-Light-Induced N-Dealkylation and C-H Activation Processes
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It has been found that the final products of the reaction of sulfonyl chlorides and tertiary amines in the presence of cadmium sulfide nanoparticles under visible light irradiation are highly dependent on the applied reaction conditions. Interestingly, with the change of a reaction condition, different pathways were conducted (visible-light-induced N-dealkylation or sp3 and sp2 C-H activation) that lead to different products such as secondary amines and various sulfonyl compounds. Remarkably, all of these reactions were performed under visible light irradiation and an air atmosphere without any additive or oxidant in benign solvents or under solvent-free conditions. During this study, the CdS nanoparticles as affordable, heterogeneous, and recyclable photocatalysts were designed, successfully synthesized, and fully characterized and applied for these protocols. During these studies, intermediates resulting from the oxidation of tertiary amines are trapped during the photoinduced electron transfer (PET) process. The reaction was carried out efficiently with a variety of substrates to give the corresponding products at relatively short times in good to excellent yields in parallel with the use of the visible light irradiation as a renewable energy source. Most of these processes are novel or are superior in terms of cost-effectiveness, safety, and simplicity to published reports.
- Firoozi, Somayeh,Hosseini-Sarvari, Mona
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p. 2117 - 2134
(2021/02/05)
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- Transition-Metal-Free and Visible-Light-Mediated Desulfonylation and Dehalogenation Reactions: Hantzsch Ester Anion as Electron and Hydrogen Atom Donor
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Novel approaches for N- and O-desulfonylation under room temperature (rt) and transition-metal-free conditions have been developed. The first methodology involves the transformation of a variety of N-sulfonyl heterocycles and phenyl benzenesulfonates to the corresponding desulfonylated products in good to excellent yields using only KOtBu in dimethyl sulfoxide (DMSO) at rt. Alternately, a visible light method has been used for deprotection of N-methyl-N-arylsulfonamides with Hantzsch ester (HE) anion serving as the visible-light-absorbing reagent and electron and hydrogen atom donor to promote the desulfonylation reaction. The HE anion can be easily prepared in situ by reaction of the corresponding HE with KOtBu in DMSO at rt. Both protocols were further explored in terms of synthetic scope as well as mechanistic aspects to rationalize key features of desulfonylation processes. Furthermore, the HE anion induces reductive dehalogenation reaction of aryl halides under visible light irradiation.
- Heredia, Micaela D.,Guerra, Walter D.,Barolo, Silvia M.,Fornasier, Santiago J.,Rossi, Roberto A.,Budén, Mariá E.
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supporting information
p. 13481 - 13494
(2020/12/15)
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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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- KMnO4-mediated oxidative C[sbnd]N bond cleavage of tertiary amines: Synthesis of amides and sulfonamides
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KMnO4-mediated oxidative C[sbnd]N bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.
- Zhang, Zhang,Liu, Yong-Hong,Zhang, Xi,Wang, Xi-Cun
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p. 2763 - 2770
(2019/04/10)
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- Charge-Transfer Complex Promoted Regiospecific C?N Bond Cleavage of Vicinal Tertiary Diamines
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A catalyst-free, charge-transfer complex promoted coupling of sulfonyl chlorides with vicinal tertiary diamines to generate sulfonamides is presented. Mechanistic studies showed that these reactions are proceeded via charge transfer of vicinal tertiary diamines to sulfonyl chlorides, forming the unstable sulfonyl quaternary ammonium like complexes which induced the regiospecific intramolecular C?N bond cleavage of vicinal tertiary diamines. (Figure presented.).
- Fu, Ying,Xu, Qin-Shan,Shi, Chun-Zhao,Du, Zhengyin,Xiao, Caiqin
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supporting information
p. 3502 - 3506
(2018/09/14)
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- Preparation method of sulfonamide compounds
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The invention provides a synthetic method of sulfonamide compounds. 1,2-dibromoethane is taken as an oxidizing agent, iodide is taken as an iodine source, sulfinate and amine compounds in the mole ratio being 2:1 are subjected to oxidative coupling in an organic solvent at 50-90 DEG C for 1-12 h, and finally, the sulfonamide compounds are obtained through purification. By adopting 1,2-dibromoethane as the oxidizing agent and iodide as the iodine source, catalytic activity, selectivity and efficiency are high; reaction conditions are mild, cost is low, yield is high, and large-scale productionis facilitated.
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Paragraph 0026
(2018/09/13)
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- NaI-Catalyzed Oxidative Amination of Aromatic Sodium Sulfinates: Synergetic Effect of Ethylene Dibromide and Air as Oxidants
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A novel NaI-catalyzed oxidative amination of sodium sulfinates, employing both ethylene dibromide (EDB) and air as the oxidants, is described. EDB was first demonstrated to be a promising mild organic oxidant that in air, converted NaI into molecular iodine to promote the cross-coupling reactions of aromatic sodium sulfinates with amines to produce arylsulfonamides. Mechanistic studies indicated that a radical pathway might be involved in the reaction process.
- Fu, Ying,Li, Quan-Zhou,Xu, Qin-Shan,Hügel, Helmut,Li, Ming-Peng,Du, Zhengyin
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supporting information
p. 6966 - 6970
(2018/11/23)
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- Mechanistic insight into thermal 1,3- and 1,5-sulfonyl migrations of N-arenesulfonylphenothiazines and N-arenesulfonylphenoxazines
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The substrate scope and mechanistic insight of the thermal-induced 1,3- and 1,5-sulfonyl migration reactions of various sulfonamides have been investigated. The results indicate that both N-arenesulfonylphenothiazines and N-arenesulfonylphenoxazines can u
- Wang, Jiandong,Son, Kwon-Il,Xu, Jiaxi
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p. 1637 - 1649
(2016/08/16)
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- Towards Uniform Iodine Catalysis: Intramolecular C?H Amination of Arenes under Visible Light
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A photochemical catalytic amination of arenes is presented. The reaction proceeds under benign iodine catalysis in the presence of visible light as the initiator and provides access to a range of differently substituted arylamines. A total of 29 examples demonstrate the broad applicability of this mild oxidation method. The scope of the reaction could further be expanded to silyl-tethered derivatives, which undergo intramolecular amination upon formation of seven-membered heterocycles. Cleavage of the silicon tether provides access to the corresponding 3-substituted anilines.
- Martínez, Claudio,Bosnidou, Alexandra E.,Allmendinger, Simon,Mu?iz, Kilian
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p. 9929 - 9932
(2016/07/19)
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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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- Sulfonamide formation from sodium sulfinates and amines or ammonia under metal-free conditions at ambient temperature
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A novel, practical and highly efficient method for the construction of a variety of sulfonamides mediated by I2 was demonstrated. The reaction proceeds readily at room temperature using a variety of sodium sulfinates and amines or ammonia in water in a metal-, base-, ligand-, or additive-free protocol. Primary, secondary and tertiary sulfonamides were obtained in good to excellent yields with a broad range of functional group tolerability. This journal is
- Yang, Kai,Ke, Miaolin,Lin, Yuanguang,Song, Qiuling
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supporting information
p. 1395 - 1399
(2015/03/18)
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- Copper-catalyzed N-arylation of sulfonamides with boronic acids in water under ligand-free and aerobic conditions
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An efficient and novel method for the copper-catalyzed arylation of sulfonamides in water under ligand-free conditions is reported. The significant advantages of this methodology are high yields, simple workup procedure, and elimination of toxic materials
- Nasrollahzadeh, Mahmoud,Ehsani, Ali,Maham, Mehdi
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p. 505 - 508
(2014/03/21)
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- Spontaneous resolution of aromatic sulfonamides: Effective screening method and discrimination of absolute structure
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(Chemical Equation Presented) An effective screening method combining parallel synthesis and solid-state CD measurements was established to identify achiral aromatic sulfonamides that show spontaneous resolution with rapidity. We found that 4 of the 12 achiral sulfonamides crystallized as chiral crystals through this method. The chirality of each sulfonamide was discriminated by solid-state CD spectra and Flack parameter in an X-ray analysis. Correspondence between the observed Cotton effect and the absolute configuration could be confirmed by time-dependent DFT calculations.
- Kato, Takako,Okamoto, Iwao,Tanatani, Aya,Hatano, Terutaka,Uchiyama, Masanobu,Kagechika, Hiroyuki,Masu, Hyuma,Katagiri, Kosuke,Tominaga, Masahide,Yamaguchi, Kentaro,Azumaya, Isao
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p. 5017 - 5020
(2007/10/03)
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- Copper-catalyzed cross-coupling of sulfonamides with aryl iodides and bromides facilitated by amino acid ligands
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A highly general, convenient, and inexpensive catalyst system was developed for the N-arylation of sulfonamides with aryl iodides or bromides by using 5-20 mol % of CuI as catalyst, 20 mol % of N-methylglycine (for aryl iodides) or N,N-dimethylglycine (for aryl bromides) as ligand, and K3PO 4 as base.
- Deng, Wei,Liu, Lei,Zhang, Chen,Liu, Min,Guo, Qing-Xiang
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p. 7295 - 7298
(2007/10/03)
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- Copper-catalyzed N-arylation of sulfonamides with aryl bromides and iodides using microwave heating
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The copper-catalyzed N-arylation of sulfonamides with a variety of aryl bromides and iodides using microwave heating is described.
- He, Huan,Wu, Yong-Jin
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p. 3385 - 3386
(2007/10/03)
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- Synthetic use of 1,1,2,2-tetraphenyldisilane for the preparation of biaryls through the intramolecular free radical ipso-substitution of N-(2-bromoaryl)arenesulfonamides
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Treatment of various N-methyl-N-(2-bromoaryl)arenesulfonamides (1a-g, 1i, and 1m) with 1,1,2,2-tetraphenyldisilane and AIBN under heating conditions gave the corresponding biaryl products (2a-g, 2i, and 2m) in moderate yields through the intramolecular radical ipso-substitution. However, N-H free N-(2-bromoaryl)arenesulfonamides 1h and 2-bromoaryl arenesulfonate 1j did not give the corresponding biarys. 1,1,2,2-Tetraphenyldisilane is the most effective reagent for 1,5-ipso-substitution on the sulfonamides among typical radical reagents such as diphenylsilane, tributyltin hydride, tris(trimethylsilyl)silane, and 1,1,2,2-tetraphenyldisilane. Furthermore, 1,1,2,2-tetraphenyldisilane has the advantages of low toxicity, stability, and ease of preparation.
- Ryokawa, Atsushi,Togo, Hideo
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p. 5915 - 5921
(2007/10/03)
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- Intermediacy of o-sulfonylium arenide ylides in the reactions of arenesulfonyl derivatives with strong bases: Insight into the puzzling rearrangement of N-arylarenesulfonamides into 2-aminodiaryl sulfones
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Benzenesulfonyl derivatives, PhSO2E, such as benzenesulfonyl fluoride, phenyl benzenesulfonate, and N-methyl-N-phenylbenzenesulfonamide, have been found to undergo ortho-lithiation with lithium 2,2,6,6-tetramethylpiperidide (LTMP) in THF at -78 °C. The resulting lithio derivatives undergo 1,3-elimination of LiE to form the transient o-sulfonylium benzenide. The latter ylide, which may be stabilized by its carbenoid character and its complexation with LiE, can be trapped by benzophenone acting as a 1,3-dipolarophile to form the adduct, 3,3-diphenyl-1,2-benzoxathiole 1,1-dioxide. The alternative formation of the latter cyclic sulfonate by reaction of the initially formed o-lithio derivative with benzophenone and by subsequent cyclization was shown not to occur. If not trapped with benzophenone, such an ylide decomposes partly into SO2 and benzyne and then undergoes self-condensation to yield poly(phenylene-o,o′-biphenylene sulfones). o-Sulfonylium benzenide also can be captured by lithium alkoxides, either present adventitously or intentionally added, to generate the corresponding alkyl benzenesulfonate. However, such alkoxides, unaided by LTMP, are themselves unable to extract an ortho-proton from benzenesulfonyl fluoride or from N-methyl-N-phenylbenzenesulfonamide to yield the corresponding o-lithio derivative. With benzenesulfonyl fluoride the lithium alkoxide can also form the sulfonate ester by direct substitution at the sulfonyl group. The Closson-Hellwinkel rearrangement of N-methyl-N-phenylbenzenesulfonamide into o-(methylamino)diphenyl sulfone by RLi or LTMP is reinterpreted as proceeding by way of the 2-lithio- or 2,6-dilithiobenzenesulfonyl derivative which eliminates lithium N-methylanilide to form the o-sulfonylium benzenide or its 6-lithio derivative. Attack of the latter ylide, acting as an electrophile, upon the ortho-position of the presumably complexed LiNMePh then consummates the rearrangement.
- Eisch, John J.,Qian, Yun,Chiu, Chingchen S.
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p. 1392 - 1398
(2007/10/03)
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- SUBSTITUENT EFFECT TREATMENT OF INTERACTIONS BETWEEN CONTIGUOUS FUNCTIONALITIES. IV. RESTRAINT TO PHENYL-NITROGEN CONJUGATIVE INTERACTION IN N-FUNCTIONALIZED N-METHYLANILINES
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13C shifts at the para position in PhN(Me)X for 17 different substituents X serve as monitors for investigating, in correlative analysis, the nature and the extent of interactions occurring between the substituent X and the N-Me cavity.For the majority of substituent, X, partitioning of the nitrogen electron pair between the phenyl and the substituent is partially hampered because of the non-zero twist angle between the planes containing the phenyl ring and the Me-N-X fragment.As a consequence, relative to PhNHX, the interactions between the cavity and the substituents are increased in intensity, especially their mesomeric component, and, at the same time, para-13C shifts are displaced toward lower field.Evidence is also provided that possible H-bonding by the NH cavity of PhNHX with dimethyl sulphoxide does not appreciably influence the substituent electron demand determined previously.
- Bradamante, Silvia,Colombo, Silvana,Pagani, Giorgio A.,Roelens, Stefano
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p. 357 - 364
(2007/10/02)
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- Heterocycles in Organic Synthesis. Part 42. Preparation of Azides, Phthalimides, and Sulphonamides from Primary Amines
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N-Alkyl and N-benzyl substituents are displaced from 2,4,6-triphenylpyridinium cations by nucleophilic azide, phthalimide, succinimide, and sulphonamide anions.This enables the conversion of primary alkyl- and benzylamines into azides, and primary (with potential for inversion or labelling) and secondary amines.
- Katritzky, Alan R.,Liso, Gaietano,Lunt, Edward,Patel, Ranjan C.,Thind, Sukhpal S.,Zia, Abid
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p. 849 - 851
(2007/10/02)
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