1210054-34-4Relevant articles and documents
Combined experimental/theoretical study on d-glucosamine promoted regioselective sulfenylation of indoles catalyzed by copper
Ge, Xin,Sun, Fengli,Liu, Xuemin,Chen, Xinzhi,Qian, Chao,Zhou, Shaodong
, p. 13175 - 13180 (2017)
A combined experimental/theoretical investigation on the d-glucosamine promoted sulfenylation of indoles at the C3 position with sodium sulfinates catalyzed by copper is presented. The C3-sulfenylation of indoles shows good functional-group tolerance and yields. The 3-I-indole was identified as a crucial intermediate in the catalytic cycle. The catalytic role of [Cu(DMSO)2]2+ was addressed using quantum chemical calculations. In the interaction of [Cu(DMSO)2]2+ with indole, the [Cu(DMSO)2]2+ complex abstracts a hydrogen from the C3 of indole. The electronic origin for selective C-H bond activation of indole was revealed.
Organophosphorus-Catalyzed Deoxygenation of Sulfonyl Chlorides: Electrophilic (Fluoroalkyl)sulfenylation by PIII/PV=O Redox Cycling
Ghosh, Avipsa,Lecomte, Morgan,Kim-Lee, Shin-Ho,Radosevich, Alexander T.
, p. 2864 - 2869 (2019)
A method for electrophilic sulfenylation by organophosphorus-catalyzed deoxygenative O-atom transfer from sulfonyl chlorides is reported. This C?S bond-forming reaction is catalyzed by a readily available small-ring phosphine (phosphetane) in conjunction with a hydrosilane terminal reductant to afford a general entry to sulfenyl electrophiles, including valuable trifluoromethyl, perfluoroalkyl, and heteroaryl derivatives that are otherwise difficult to access. Mechanistic investigations indicate that the twofold deoxygenation of the sulfonyl substrate proceeds by the intervention of an off-cycle resting state thiophosphonium ion. The catalytic method represents an operationally simple protocol using a stable phosphine oxide as a precatalyst and exhibits broad functional-group tolerance.
Synergistic Effect of Squaric Acid in Bromine-Catalyzed Deoxygenation of Sulfonyl Derivatives: Mechanistic Investigations and Synthetic Applications in Electrophilic (Fluoroalkyl)sulfenylation
Xiang, Haonan,Liu, Jie,Wang, Jieping,Jiang, Lvqi,Yi, Wenbin
supporting information, p. 181 - 185 (2021/12/17)
A method for electrophilic (fluoroalkyl)sulfenylation of nucleophiles by collaborative CTAB- and squaric acid-promoted deoxygenation of sulfonyl derivatives is reported. Mechanistic studies indicate that squaric acid dramatically decreased the energy barr
Flavin/I2-Catalyzed Aerobic Oxidative C–H Sulfenylation of Aryl-Fused Cyclic Amines
Jiang, Xinpeng,Zhao, Zongchen,Shen, Zhifeng,Chen, Keda,Fang, Liyun,Yu, Chuanming
, p. 3889 - 3895 (2020/06/01)
We report an aerobic oxidative C–H sulfenylation of aryl-fused cyclic amines with various thiols catalyzed by flavin/I2 for the first time. While flavin I catalyzed the C–H sulfenylation of indolines to afford 3-sulfenylindoles, flavin II enabl
Iodine/Manganese Catalyzed Sulfenylation of Indole via Dehydrogenative Oxidative Coupling in Anisole
Li, Weihe,Wang, Hao,Liu, Shengping,Feng, Hua,Benassi, Enrico,Qian, Bo
, p. 2666 - 2671 (2020/05/25)
This protocol describes an iodine/manganese catalytic system for dehydrogenative oxidative coupling reaction of indoles with thiols in anisole. Particularly, the dual roles of anisole have been first demonstrated as a solvent and as a promoter via the formation of an oxonium ion intermediate to accelerate the generation of products. A series of sulfenylindoles are readily constructed under aerobic mild reaction conditions. In addition, the achievement for preparing anticancer and anti-AIDS drugs testifies the practicability of this approach. The mechanism studies disclose probable alternative pathways and a single-electron transfer process are involved in this transformation. (Figure presented.).
Domino C?S/C?N Bond Formation Using Well-Defined Copper-Phosphine Complex Catalyst: Divergent Approach to 3-Sulfenylated Indoles
Tamargo, Ramuel John Inductivo,Kim, Sung Hong,Lee, Yong Rok
, p. 4005 - 4015 (2019/07/18)
A protocol was developed for the synthesis of 3-thioindoles in good-to-excellent yields involving sulfenylation between 2-nitrocinnamaldehydes and various thiols using a well-defined copper(I)-phosphine complex catalyst. This unconventional divergent approach involves in situ generation of indoles via domino C?S/C?N bond formation initiated by sulfa-Michael addition followed by intramolecular N-heteroannulation. This protocol shows good chemoselectivity and broad substrate scope. To briefly demonstrate the value of this approach, 2-benzoyl-3-sulfenylated indoles were prepared from commercially available 2-nitrochalcones and thiols. (Figure presented.).
NH4I/1,10-phenanthroline catalyzed direct sulfenylation of N-heteroarenes with ethyl arylsulfinates
Chen, Lingjuan,Zhang, Jun,Wei, Yueting,Yang, Zhen,Liu, Ping,Zhang, Jie,Dai, Bin
, (2019/10/14)
An efficient synthesis of N-heterocyclic aryl sulfides via NH4I/1,10-phenanthroline-catalyzed direct sulfenylation reactions was reported. In this reaction, heteroarenes such as indoles, and pyrroles serve as nucleophiles by installing a arylthio group at the C3 and C2 position of heterocycles, respectively. With readily accessible and free of unpleasant odor ethyl arylsulfinates as sulfur reagents, the metal-free-catalyzed direct sulfenylation of N-heteroarenes has been developed. 3-Arylthio-indoles and 2-arylthio-pyrroles derivatives were obtained in moderate to excellent yields, even on gram scale. The reaction was general for a broad scope of substrates and demonstrated good tolerance to a variety of functional groups.
Synergistic Dual Role of [hmim]Br-ArSO2Cl in Cascade Sulfenylation-Halogenation of Indole: Mechanistic Insight into Regioselective C-S and C-S/C-X (X = Cl and Br) Bond Formation in One Pot
Equbal, Danish,Singh, Richa,Saima,Lavekar, Aditya G.,Sinha, Arun K.
, p. 2660 - 2675 (2019/03/14)
Bifunctionalized indoles are an important class of biologically active heterocyclic compounds and potential drug candidates. Because of the lack of efficient synthetic methods, one pot cascade synthesis of these compounds is rare and remains a challenge.
Fe(III)-Catalyzed direct C3 chalcogenylation of indole: The effect of iodide ions
Luz, Eduardo Q.,Seckler, Diego,Araújo, Janylson Souza,Angst, Leonardo,Lima, David B.,Maluf Rios, Elise Ane,Ribeiro, Ronny R.,Rampon, Daniel S.
supporting information, p. 1258 - 1266 (2019/02/03)
A mild and efficient iron (III)-catalyzed C3 chalcogenylation of indoles has been developed and the role of the iodide ions in this transformation was investigated. EPR experiments revealed the reduction of Fe(III) to Fe(II) under the reaction conditions, supporting the formation of molecular iodine in the system, which in effect catalyze the reaction. The scope of the chalcogenylation was broad and the synthesis of more functionalized 3-selenylindoles was explored.
Catalyst-free sulfenylation of indoles with sulfinic esters in ethanol
Yang, Xiuqin,Bao, Yishu,Dai, Zonghao,Zhou, Qingfa,Yang, Fulai
supporting information, p. 3727 - 3731 (2018/08/21)
A novel catalyst-free method for the synthesis of structurally diverse indole thioethers in moderate to excellent yields has been developed. In this reaction, sulfinic esters serve as new sulfur electrophiles.
