15183-74-1Relevant academic research and scientific papers
Cu-catalyzed couplings of aryl iodonium salts with sodium trifluoromethanesulfinate
Cullen, Steven C.,Shekhar, Shashank,Nere, Nandkishor K.
, p. 12194 - 12201 (2013)
A convenient method for the preparation of aryl trifluoromethylsulfones from the reactions of diaryliodonium salts with sodium trifluoromethanesulfinate in the presence of copper catalysts is described. Cuprous oxide in DMF was found to be the optimal catalyst for the reaction. The reaction conditions are tolerant of various functional groups as well as of various counteranions of the iodonium salt. The synthetic utility of the process is demonstrated by performing the reaction on a preparative scale (88 g).
Practical and efficient synthesis of aryl trifluoromethyl sulfones from arylsulfonyl chlorides with Umemoto's reagent II
Zhou, Xiaocong,Hu, Dufen,He, Xinyi,Li, Yuanqiang,Chu, Youqun,She, Yuanbin
supporting information, (2019/12/24)
A practical and efficient method for the synthesis of aryl trifluoromethyl sulfones has been developed by a tandem reaction of arylsulfonyl chlorides with Umemoto's reagent II. The advantageous features of this method are simple operation, mild reaction conditions, wide scope of substrates, high yield of products, and easy scalability.
Arenesulfonyl Fluoride Synthesis via Copper-Catalyzed Fluorosulfonylation of Arenediazonium Salts
Liu, Yongan,Yu, Donghai,Guo, Yong,Xiao, Ji-Chang,Chen, Qing-Yun,Liu, Chao
supporting information, p. 2281 - 2286 (2020/03/13)
We report herein a general and practical copper-catalyzed fluorosulfonylation reaction of a wide range of abundant arenediazonium salts to smoothly prepare various arenesulfonyl fluorides using the 1,4-diazabicyclo[2.2.2]octane-bis(sulfur dioxide) adduct as a convenient sulfonyl source in combination with KHF2 as an ideal fluorine source and without the need for additional oxidants. Interestingly, the electronic character of the arene ring in the starting arenediazonium salts has a significant impact on the reaction mechanistic pathway.
Cross-Coupling of Aryl Trifluoromethyl Sulfones with Arylboronates by Cooperative Palladium/Rhodium Catalysis
Fukuda, Jun-Ichi,Nogi, Keisuke,Yorimitsu, Hideki
supporting information, p. 8987 - 8991 (2019/11/11)
The Suzuki-Miyaura arylation of aryl trifluoromethyl sulfones via C-SO2 bond cleavage has been developed by means of cooperative palladium/rhodium catalysis. A series of aryl trifluoromethyl sulfones and arylboronic acid neopentylglycol esters are converted to the corresponding biaryls. Mechanistic investigations suggest that (1) the rhodium catalyst mediates the transfer of the aryl ring from arylboronate to palladium, resulting in the acceleration of the transmetalation step, and (2) the C-C bond-forming reductive elimination step is the turnover-limiting step.
Bifluoride Ion Mediated SuFEx Trifluoromethylation of Sulfonyl Fluorides and Iminosulfur Oxydifluorides
Smedley, Christopher J.,Zheng, Qinheng,Gao, Bing,Li, Suhua,Molino, Andrew,Duivenvoorden, Hendrika M.,Parker, Belinda S.,Wilson, David J. D.,Sharpless, K. Barry,Moses, John E.
supporting information, p. 4552 - 4556 (2019/03/07)
SuFEx is a new-generation click chemistry transformation that exploits the unique properties of S?F bonds and their ability to undergo near-perfect reactions with nucleophiles. We report here the first SuFEx-based procedure for the efficient synthesis of pharmaceutically important triflones and bis(trifluoromethyl)sulfur oxyimines from sulfonyl fluorides and iminosulfur oxydifluorides, respectively. The new process involves rapid S?F exchange with trifluoromethyltrimethylsilane (TMSCF3) upon activation by potassium bifluoride in anhydrous DMSO. The reaction tolerates a wide selection of substrates and proceeds under mild conditions without need for chromatographic purification. A tentative mechanism is proposed involving nucleophilic displacement of S?F by the trifluoromethyl anion via a five-coordinate intermediate. The utility of late-stage SuFEx trifluoromethylation is demonstrated through the synthesis and selective anticancer properties of a bis(trifluoromethyl)sulfur oxyimine.
Synthesis of Aryl Triflones through the Trifluoromethanesulfonylation of Benzynes
Sumii, Yuji,Sugita, Yutaka,Tokunaga, Etsuko,Shibata, Norio
, p. 204 - 211 (2018/03/02)
The direct synthesis of aryl triflones, that is, trifluoromethanesulfonyl arenes, was achieved through the trifluoromethanesulfonylation of benzynes. The trifluoromethanesulfonyl group, one of the fluorinated functional groups, is a highly electron-negative and mild lipophilic substituent. Aryl triflones have high potential in the synthesis of bioactive compounds and specialty materials. The treatment of 2-(trimethylsilyl)aryl trifluoromethanesulfonates with cesium fluoride in the presence of 15-crown-5 generated benzynes, which reacted with sodium trifluoromethanesulfinate followed by protonation with tBuOH under heating conditions, provided aryl triflones in moderated to good yields. Both symmetrical and unsymmetrical triflones were nicely accessed under the same reaction conditions. Interestingly, the trifluoromethanesulfonylation of unsymmetrical benzyne precursors proceeded smoothly to furnish corresponding aryl triflones in good yields with good to high regioselectivities. The balance of polarization of electric charge as well as steric hindrance of the benzyne intermediates are central factors to control the outcome of regioselectivity.
Copper-Mediated Di- and Monofluoromethanesulfonylation of Arenediazonium Tetrafluoroborates: Probing the Fluorine Effect
Xing, Bo,Ni, Chuanfa,Hu, Jinbo
, p. 206 - 212 (2018/02/06)
A copper-mediated di- and monofluoromethanesulfonylation of arenediazonium tetrafluoroborates using di- and monofluoromethanesulfinate reagents provides aryl difluoromethyl (or monofluoromethyl) sulfones in good yields. It was found that the relative reactivity of these sodium fluoroalkanesulfinates in the present reactions decreases in the following order: CH2FSO2Na > CF2HSO2Na > CF3SO2Na.
A method of manufacturing a benzene derivative (trifluoromethylsulfonyl)
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Paragraph 0055; 0056, (2016/10/08)
PROBLEM TO BE SOLVED: To provide a method for producing a (trifluoromethylsulfonyl)benzene derivative which is useful as a medicine, an agricultural chemical, a functional material and a production intermediate thereof. SOLUTION: In this method, a (trifluoromethylsulfonyl)benzene derivative is produced by reacting diaryliodonium salt represented by general formula (1) with trifluoromethanesulfinic acid salt in the presence of a copper (I) salt. (In the formula, R1, R2, R3, R4, R5, R6, R7, R8, R9and R10each independently represents a hydrogen atom, a 1-6C alkyl group, a 1-6C haloalkyl group, a 1-6C alkoxy group, a 2-6C acyl group, (1-5C alkoxy)carbonyl group, a nitro group, a cyano group, a chlorine atom or a bromine atom). COPYRIGHT: (C)2013,JPOandINPIT
Pd-catalyzed synthesis of aryl and heteroaryl triflones from reactions of sodium triflinate with aryl (heteroaryl) triflates
Smyth, Lynette A.,Phillips, Eric M.,Chan, Vincent S.,Napolitano, José G.,Henry, Rodger,Shekhar, Shashank
, p. 1285 - 1294 (2016/02/19)
A novel method for Pd-catalyzed triflination of aryl and heteroaryl triflates using NaSO2CF3 as the nucleophile is described. The combination of Pd2(dba)3 and RockPhos formed the most effective catalyst. A broad range of functional groups and heteroaromatic compounds were tolerated under the neutral reaction conditions. The order of reactivity ArOTf ≥ ArCl ≥ ArBr is consistent with transmetalation being a slow step of the reaction.
Copper-catalyzed trifluoromethylation of arylsulfinate salts using an electrophilic trifluoromethylation reagent
Lin, Xiaoxi,Wang, Guimei,Li, Huaifeng,Huang, Yuanyuan,He, Weiming,Ye, Dandan,Huang, Kuo-Wei,Yuan, Yaofeng,Weng, Zhiqiang
, p. 2628 - 2632 (2013/03/29)
A copper-catalyzed method for the trifluoromethylation of arylsulfinates with Togni's reagent has been developed, affording aryltrifluoromethylsulfones in moderate to good yields. A wide range of functional groups in arylsulfinates are compatible with the
