719-98-2Relevant articles and documents
Synthesis method of phthalimide type trifluoromethyl sulfuration reagent
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Paragraph 0016, (2021/06/02)
The invention belongs to the technical field of synthesis of organic compounds, and relates to a synthesis method of a phthalimide type trifluoromethyl sulfide reagent. The structural general formula of the reagent is as shown in the formula (1). The synthesis method of the phthalimide type trifluoromethyl sulfide reagent comprises the following steps: by taking a nitrogen halogenated compound containing a phthalimide structural framework, trifluoromethanesulfonate, nonafluorobutyl sulfonate, methanesulfonate and p-toluenesulfonate as reaction substrates, phthalimide type trifluoromethyl sulfuration reagent is synthesized by taking trifluoromethylthioester as a trifluoromethylthio source. According to the preparation method, trifluoromethylthioester is taken as a trifluoromethylthio source, trifluoromethylthio negative ions are generated under activation of fluorine negative ions, nucleophilic substitution is carried out on the reaction substrates, so that construction of a nitrogen-sulfur bond is realized, and the phthalimide type trifluoromethyl sulfuration reagent is obtained after separation and purification. According to the synthesis method of the phthalimide type trifluoromethyl sulfuration reagent, the raw materials are easy to prepare, the reaction reagent is low in price, the synthesis cost of the phthalimide type trifluoromethyl sulfide reagent is remarkably reduced, and industrial production is facilitated; synthesis conditions are mild, and operation is simple and safe; transition metal elements are not needed, and the method is green and environment-friendly.
Photocatalyzed Radical Relayed Regio- And Stereoselective Trifluoromethylthiolation-Boration
Zhang, Qiang,Li, Xiaojuan,Zhang, Weigang,Wang, Yi,Pan, Yi
supporting information, p. 5410 - 5414 (2021/07/21)
Vinylboronates and alkylboronates are key components in variegated transformations in all aspects of chemical science. This work describes a sequential radical difunctionalization strategy for the construction of fluorine-containing vinylboronates and alkylboronates with the integrated redox-active reagent N-trifluoromethylthiophthalimide. This multifunctional N-S precursor offers a scalable and practical protocol for the trifluoromethylthiolation-borylation of unsaturated hydrocarbons in a highly regio- and stereoselective fashion, which can be further converted into valuable synthons via boryl migration.
Exploration of the Synthetic Potential of Electrophilic Trifluoromethylthiolating and Difluoromethylthiolating Reagents
Zhang, Jingjing,Yang, Jin-Dong,Zheng, Hanliang,Xue, Xiao-Song,Mayr, Herbert,Cheng, Jin-Pei
supporting information, p. 12690 - 12695 (2018/09/25)
The electrophilicity parameters (E) of some trifluoromethylthiolating and difluoromethylthiolating reagents were determined by following the kinetics of their reactions with a series of enamines and carbanions with known nucleophilicity parameters (N, sN), using the linear free-energy relationship log k2=sN(N+E). The electrophilic reactivities of these reagents cover a range of 17 orders of magnitude, with Shen and Lu's reagent 1 a being the most reactive and Billard's reagent 1 h being the least reactive electrophile. While the observed electrophilic reactivities (E) of the amido-derived trifluoromethylthiolating reagents correlate well with the calculated Gibbs energies for heterolytic cleavage of the X?SCF3 bonds (Tt+DA), the cumol-derived reagents 1 f and 1 g are more reactive than expected from the thermodynamics of the O?S cleavage. The E parameters of the tri/difluoromethylthiolating reagents derived in this work provide an ordering principle for their use in synthesis.
