2002-89-3Relevant academic research and scientific papers
Gold (I/III)-Catalyzed Trifluoromethylthiolation and Trifluoromethylselenolation of Organohalides
Mudshinge, Sagar R.,Yang, Yuhao,Xu, Bo,Hammond, Gerald B.,Lu, Zhichao
, (2022/02/10)
The first C?SCF3/SeCF3 cross-coupling reactions using gold redox catalysis [(MeDalphos)AuCl], AgSCF3 or Me4NSeCF3, and organohalides as substrates are reported. The new methodology enables a one-stop shop synthesis of aryl/alkenyl/alkynyl trifluoromethylthio- and selenoethers with a broad substrate scope (>60 examples with up to 97 % isolated yield). The method is scalable, and its robustness is evidenced by the late-stage functionalization of various bioactive molecules, which makes this reaction an attractive alternative in the synthesis of trifluoromethylthio- and selenoethers for pharmaceutical and agrochemical research and development.
Efficient Synthesis of 5-Trifluoromethylthio-1,2,3-Triazoles: One-Pot Multicomponent Reaction from Elemental Sulfur and TMSCF 3
Li, Meng-Tian,Shen, Liang-Liang,Wu, Qin-Pei,Zhang, Lin-Lin
supporting information, p. 304 - 310 (2019/12/30)
A sequential multistep reaction toward 5-trifluoromethyl thio-1,2,3-triazoles has been established, starting from alkynes, organo azides, S 8, and (trifluoromethyl)trimethylsilane (TMSCF 3). This reaction features mild conditions, easy operation, and readily available substrates.
Rhodium(I)-Catalyzed Regioselective Azide-internal Alkynyl Trifluoromethyl Sulfide Cycloaddition and Azide-internal Thioalkyne Cycloaddition under Mild Conditions
Song, Wangze,Zheng, Nan,Li, Ming,He, Junnan,Li, Junhao,Dong, Kun,Ullah, Karim,Zheng, Yubin
supporting information, p. 469 - 475 (2019/01/04)
A regioselective method to access fully substituted 5-trifluoromethylthio-1,2,3-triazoles and 5-thio-1,2,3-triazoles from the internal alkynyl trifluoromethyl sulfides and internal thioalkynes by a rhodium(I)-catalyzed azide-alkyne cycloaddition (RhAAC) reaction under mild conditions has been developed. This approach features good compatibility with water and air, a broad substrate scope, good functional group tolerance, high yields and excellent regioselectivities. The high 1,5-regioselectivities were controlled by the strong coordination between the sulfur atom and the π-acidic rhodium. The advantages of this method further include its applicability to gram-scale preparation, the use of solid-phase synthesis technique, and the mutually orthogonal CuAAC-RhAAC reaction. (Figure presented.).
Copper-Catalyzed, Stereoselective Bis-trifluoromethylthiolation of Propiolic Acid Derivatives with AgSCF3
Pan, Shen,Li, Huan,Huang, Yangen,Xu, Xiu-Hua,Qing, Feng-Ling
, p. 3247 - 3250 (2017/06/23)
A copper-catalyzed chemo- and stereoselective oxidative bis-trifluoromethylthiolation of propiolic acid derivatives was achieved by using carboxylic acid as the activating group and formic acid as a cosolvent. The reaction of propiolic acid derivatives and AgSCF3 in the presence of (NH4)2S2O8 and catalytic Cu(OAc)2 in MeCN/HCO2H afforded bis-trifluoromethylthiolated acrylic acids in moderate to excellent yields with E selectivity. Further derivatization of the resultant products gave a series of polysubstituted SCF3-containing alkenes.
Copper-Catalyzed Perfluoroalkylthiolation of Alkynes with Perfluoroalkanesulfenamides
Tlili, Anis,Alazet, Sébastien,Glenadel, Quentin,Billard, Thierry
supporting information, p. 10230 - 10234 (2016/07/19)
Copper-catalyzed direct perfluoroalkylthiolation of alkynes by using the corresponding perfluoroalkanesulfenamide reagent is reported. The selective mono- and bis-perfluoroalkylthiolation of alkynes can be conducted under very mild conditions (no base, room temperature) in very good to excellent yields. This approach, which uses a low toxicity, inexpensive copper catalyst that incorporates a commercially available ligand, is applied in the absence of any additional base. Preliminary mechanistic investigations shed some light on the nature of the unprecedented reactivity observed.
Expeditious trifluoromethylthiolation and trifluoromethylselenolation of alkynyl(phenyl)iodoniums by [XCF3]? (X = S, Se) anions
Fang, Wan-Yin,Dong, Tao,Han, Jia-Bin,Zha, Gao-Feng,Zhang, Cheng-Pan
supporting information, p. 11502 - 11509 (2016/12/16)
Trifluoromethylthiolation and trifluoromethylselenolation of alkynyl(phenyl)iodonium tosylates by [XCF3]? (X = S, Se) ions was accomplished in 5-10 minutes at room temperature under a N2 atmosphere and provided a variety of alkynyl trifluoromethyl sulfides and selenides in good yields. Compared to the known methods, this approach has several advantages such as short reaction times and metal- and additive-free conditions without needing excess [Me4N][XCF3] reagents. Moreover, the less efficient reactions of (phenylethynyl)benziodoxol(on)e with [Me4N][XCF3] under the standard conditions demonstrate that acyclic alkynyl(phenyl)iodoniums are more powerful alkynyl sources in the conversion. This protocol allows for a fast and convenient access to numerous alkynyl trifluoromethyl sulfides and selenides.
First and second generation of trifluoromethanesulfenamide reagent: A trifluoromethylthiolating comparison
Glenadel, Quentin,Alazet, Sébastien,Billard, Thierry
, p. 89 - 95 (2015/11/09)
Trifluoromethylthiolation of molecules is a more and more studied reaction. In particular, the direct electrophilic trifluoromethylthiolation plays an important role in this chemistry. Among the various developed reagents, trifluoromethanesulfenamides constitute an efficient family of reagents. However, no systematic comparison of these two generations has been realized. In this paper, the difference of reactivity of these reagents is studied towards various nucleophiles.
Structure-reactivity relationship of trifluoromethanesulfenates: Discovery of an electrophilic trifluoromethylthiolating reagent
Shao, Xinxin,Xu, Chunfa,Lu, Long,Shen, Qilong
, p. 3012 - 3021 (2015/03/30)
A family of electrophilic trifluoromethanesulfenates was prepared. Structure-reactivity relationship studies showed that the substituted groups on the aryl ring of the trifluoromethylthiolating reagent did not have an obvious influence on their reactivities. A simplified electrophilic trifluoromethylthiolating reagent 1c was then identified that can react with a wide range of nucleophiles such as Grignard reagents, arylboronic acids, alkynes, indoles, β-ketoesters, oxindoles, and sodium sulfinates under mild reaction conditions. A variety of functional groups were tolerated under these conditions.
A concise synthesis of (alkynyl)(trifluoromethyl)sulfanes via a bismuth(iii)-promoted reaction of trimethyl(alkynyl)silane with trifluoromethanesulfanylamide
Sheng, Jie,Wu, Jie
supporting information, p. 7629 - 7633 (2014/12/11)
A bismuth(iii)-promoted reaction of trimethyl(alkynyl)silanes with trifluoromethanesulfanylamide is developed, giving rise to (alkynyl)(trifluoromethyl)sulfanes in good yields.
Oxidative trifluoromethylthiolation of terminal alkynes with AgSCF 3: A convenient approach to alkynyl trifluoromethyl sulfides
Zhu, Sheng-Qing,Xu, Xiu-Hua,Qing, Feng-Ling
supporting information, p. 4453 - 4456 (2014/08/05)
A new method for the efficient synthesis of alkynyl trifluoromethyl sulfides was developed. By combining AgSCF3 and NCS in N,N-dimethylacetamide, an electrophilic active intermediate was produced, which was then treated with a variety of terminal alkynes to afford the corresponding trifluoromethanesulfenylated products in moderate to excellent yields. A new oxidative trifluoromethylthiolation system, AgSCF3/NCS, is developed and applied in the efficient synthesis of alkynyl trifluoromethyl sulfides. Various desired compounds are obtained under mild conditions in moderate to excellent yields. Copyright
