90-10-8Relevant academic research and scientific papers
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
Firoozi, Somayeh,Hosseini-Sarvari, Mona
, p. 2117 - 2134 (2021/02/05)
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.
Transition-Metal-Free and Visible-Light-Mediated Desulfonylation and Dehalogenation Reactions: Hantzsch Ester Anion as Electron and Hydrogen Atom Donor
Heredia, Micaela D.,Guerra, Walter D.,Barolo, Silvia M.,Fornasier, Santiago J.,Rossi, Roberto A.,Budén, Mariá E.
supporting information, p. 13481 - 13494 (2020/12/15)
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.
KMnO4-mediated oxidative C[sbnd]N bond cleavage of tertiary amines: Synthesis of amides and sulfonamides
Zhang, Zhang,Liu, Yong-Hong,Zhang, Xi,Wang, Xi-Cun
, p. 2763 - 2770 (2019/04/10)
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.
Hypervalent Iodine Mediated Sulfonamide Synthesis
Poeira, Diogo L.,Macara, Jo?o,Faustino, Hélio,Coelho, Jaime A. S.,Gois, Pedro M. P.,Marques, M. Manuel B.
supporting information, p. 2695 - 2701 (2019/04/08)
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.
Charge-Transfer Complex Promoted Regiospecific C?N Bond Cleavage of Vicinal Tertiary Diamines
Fu, Ying,Xu, Qin-Shan,Shi, Chun-Zhao,Du, Zhengyin,Xiao, Caiqin
supporting information, p. 3502 - 3506 (2018/09/14)
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.).
Preparation method of sulfonamide compounds
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Paragraph 0026, (2018/09/13)
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.
NaI-Catalyzed Oxidative Amination of Aromatic Sodium Sulfinates: Synergetic Effect of Ethylene Dibromide and Air as Oxidants
Fu, Ying,Li, Quan-Zhou,Xu, Qin-Shan,Hügel, Helmut,Li, Ming-Peng,Du, Zhengyin
supporting information, p. 6966 - 6970 (2018/11/23)
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.
Mechanistic insight into thermal 1,3- and 1,5-sulfonyl migrations of N-arenesulfonylphenothiazines and N-arenesulfonylphenoxazines
Wang, Jiandong,Son, Kwon-Il,Xu, Jiaxi
, p. 1637 - 1649 (2016/08/16)
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
Towards Uniform Iodine Catalysis: Intramolecular C?H Amination of Arenes under Visible Light
Martínez, Claudio,Bosnidou, Alexandra E.,Allmendinger, Simon,Mu?iz, Kilian
, p. 9929 - 9932 (2016/07/19)
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.
Metal-free direct construction of sulfonamides via iodine- mediated coupling reaction of sodium sulfinates and amines at room temperature
Wei, Wei,Liu, Chunli,Yang, Daoshan,Wen, Jiangwei,You, Jinmao,Wang, Hua
supporting information, p. 987 - 992 (2015/03/30)
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%).
