1736-75-0Relevant academic research and scientific papers
Sandmeyer trifluoromethylthiolation of arenediazonium salts with sodium thiocyanate and Ruppert-Prakash reagent
Danoun, Gregory,Bayarmagnai, Bilguun,Gruenberg, Matthias F.,Goossen, Lukas J.
, p. 1312 - 1316 (2014)
In the presence of copper thiocyanate, sodium thiocyanate and the inexpensive, easy-to-use trifluoromethylating reagent Me3Si-CF 3, diazonium salts are smoothly converted into the corresponding aryl trifluoromethyl thioethers. Combin
Trifluoromethyl Sulfoxides: Reagents for Metal-Free C?H Trifluoromethylthiolation
Carlton, C. Grace,McDouall, Joseph J. W.,Perry, Gregory J. P.,Procter, David J.,Tayu, Masanori,Wang, Dong
supporting information, p. 15918 - 15922 (2020/07/20)
Trifluoromethyl sulfoxides are a new class of trifluoromethylthiolating reagent. The sulfoxides engage in metal-free C?H trifluoromethylthiolation with a range of (hetero)arenes. The method is also applicable to the functionalization of important compound classes, such as ligand derivatives and polyaromatics, and in the late-stage trifluoromethylthiolation of medicines and agrochemicals. The isolation and characterization of a sulfonium salt intermediate supports an interrupted Pummerer reaction mechanism.
Diversification of Trifluoromethylthiolation of Aromatic Molecules with Derivatives of Trifluoromethanesulfenamide
Horvat, Monika,Jereb, Marjan,Iskra, Jernej
supporting information, p. 3837 - 3843 (2018/07/31)
Trifluoromethylthiolation of aromatic compounds with different electrophilic reagents of the type ArNHSCF3 was studied in the presence of triflic acid as an activator. The effect of the reagent structure on the reactivity was studied with three different reagents: PhNHSCF3 (H/SCF3, 1a), 4-ClC6H4NHSCF3 (Cl/SCF3, 1b) and C6F5NHSCF3 (F5/SCF3, 1c). p-Chloro substituted reagent 1b was more stable than the unsubstituted 1a and was the most effective because it could not react by trifluoromethylthiolation of itself. This reaction was the most important side reaction of 1a. The pentafluoro derivative 1c was less reactive. Solvent played an important role in the transformation and, depending on the substrate, dichloromethane, hexane or trifluoroacetic acid gave the best yield of various trifluoromethylthiolated aromatic molecules (63–98 %).
Metal-free trifluoromethylthiolation of arenediazonium salts with Me4NSCF3
Bertoli, Giulia,Exner, Benjamin,Evers, Mathies V.,Tschulik, Kristina,Goo?en, Lukas J.
, p. 132 - 136 (2018/04/05)
A metal-free entry to the pharmaceutically meaningful substrate class of trifluoromethyl thioethers has been developed starting from widely available arenediazonium salts and commercially available Me4N+SCF3?. This reaction proceeds within one hour at 0 °C and is applicable to a wide range of functionalized substrates.
Triphenylphosphine-Mediated Deoxygenative Reduction of CF3SO2Na and Its Application for Trifluoromethylthiolation of Aryl Iodides
Yang, Yi,Xu, Long,Yu, Siqi,Liu, Xiaoqiang,Zhang, Yu,Vicic, David A.
supporting information, p. 858 - 863 (2016/01/16)
We report herein a practical method for taming Langlois' reagent CF3SO2Na to generate CuSCF3 by a triphenylphospine-mediated deoxygenative reduction process. This chemistry highlights a novel utilization of the inherent CF3S skeleton of Langlois' reagent as a CF3S feedstock under mild conditions. The CuSCF3 intermediate generated by this protocol can react with a wide array of supporting ligands to furnish several air-stable [LCu(SCF3)] complexes as valuable trifluoromethylthiolating agents. In addition, the CuSCF3 intermediate can be directly employed for the trifluoromethylthiolation of (hetero)aryl iodides with operational simplicity and atomic efficiency. Efficient synthesis! A low cost method for the generation of CuSCF3 by a triphenylphospine-mediated deoxygenative reduction of Langlois' reagent (CF3SO2Na) has been developed (see scheme). This method can be applied for the convenient synthesis of a wide array of ligated and air-stable CuSCF3 complexes. Additionally, the CuSCF3 complexes generated in situ by this protocol were found to trifluoromethylthiolate (hetero)aryl iodides with high efficiency.
Copper-Mediated Oxidative Trifluoromethylthiolation of Potassium Aryltrifluoroborates with Elemental Sulfur and Ruppert-Prakash Reagent
Dubbaka, Srinivas Reddy,Atthunuri, Azmi Reddy,Prakash, Koraboina Chandra,Rangabashyam, Prabhu,Gadde, Satyanarayana,Kothandaraman, Rajesh
supporting information, p. 1246 - 1252 (2016/05/09)
A facile procedure for the copper-mediated oxidative trifluoromethylthiolation of potassium aryl- and heteroaryltrifluoroborates with Ruppert-Prakash reagent and elemental sulfur is presented. Aryl trifluoromethyl thioethers can be prepared in good to mod
Sandmeyer-Type Trifluoromethylthiolation and Trifluoromethylselenolation of (Hetero)Aromatic Amines Catalyzed by Copper
Matheis, Christian,Wagner, Victoria,Goossen, Lukas J.
supporting information, p. 79 - 82 (2016/01/25)
Aromatic and heteroaromatic diazonium salts were efficiently converted into the corresponding trifluoromethylthio- or selenoethers by reaction with Me4NSCF3 or Me4NSeCF3, respectively, in the presence of catalytic amounts of copper thiocyanate. These Sandmeyer-type reactions proceed within one hour at room temperature, are applicable to a wide range of functionalized molecules, and can optionally be combined with the diazotizations into one-pot protocols.
Copper-Catalyzed Trifluoromethylthiolation of Di(hetero)aryl-λ3-iodanes: Mechanistic Insight and Application to Synthesis of (Hetero)Aryl Trifluoromethyl Sulfides
Saravanan, Perumal,Anbarasan, Pazhamalai
supporting information, p. 3521 - 3528 (2016/01/25)
The direct and regioselective copper/S-Phos-catalyzed trifluoromethylthiolation of symmetrical and unsymmetrical di(hetero)aryl-λ3-iodanes has been accomplished for the synthesis of various (hetero)aryl trifluoromethyl sulfides employing readily accessible silver trifluoromethylthiolate (AgSCF3) as nucleophilic trifluoromethylthiolating reagent. The developed transformation tolerates various functional groups like nitrile, enolizable ketone, ester, nitro and free carboxylic acid. Interestingly, the formal trifluoromethylthiolation of arenes was also achieved through integration of the synthesis of diaryl-λ3-iodanes from arenes with the trifluoromethylthiolation. Mechanistic investigations did not favor the radical formation and SET pathway. Based on the variable temperature 19F NMR spectroscopy, isolation of the most relevant catalytic intermediate, and stoichiometric studies supported the Cu(I)/Cu(III) catalytic cycle, wherein the oxidative addition of diaryl-λ3-iodanes was assisted by the silver salt.
Fundamental studies and development of nickel-catalyzed trifluoromethylthiolation of aryl chlorides: Active catalytic species and key roles of ligand and traceless MeCN additive revealed
Yin, Guoyin,Kalvet, Indrek,Englert, Ulli,Schoenebeck, Franziska
supporting information, p. 4164 - 4172 (2015/04/14)
A catalytic protocol to convert aryl and heteroaryl chlorides to the corresponding trifluoromethyl sulfides is reported herein. It relies on a relatively inexpensive Ni(cod)2/dppf (cod = 1,5-cyclooctadiene; dppf = 1,1′-bis(diphenylphosphino)ferrocene) catalyst system and the readily accessible coupling reagent (Me4N)SCF3. Our computational and experimental mechanistic data are consistent with a Ni(0)/Ni(II) cycle and inconsistent with Ni(I) as the reactive species. The relevant intermediates were prepared, characterized by X-ray crystallography, and tested for their catalytic competence. This revealed that a monomeric tricoordinate Ni(I) complex is favored for dppf and Cl whose role was unambiguously assigned as being an off-cycle catalyst deactivation product. Only bidentate ligands with wide bite angles (e.g., dppf) are effective. These bulky ligands render the catalyst resting state as [(P-P)Ni(cod)]. The latter is more reactive than Ni(P-P)2, which was found to be the resting state for ligands with smaller bite angles and suffers from an initial high-energy dissociation of one ligand prior to oxidative addition, rendering the system unreactive. The key to effective catalysis is hence the presence of a labile auxiliary ligand in the catalyst resting state. For more challenging substrates, high conversions were achieved via the employment of MeCN as a traceless additive. Mechanistic data suggest that its beneficial role lies in decreasing the energetic span, therefore accelerating product formation. Finally, the methodology has been applied to synthetic targets of pharmaceutical relevance.
Copper-mediated oxidative trifluoromethylthiolation of aryl boronic acids with CF3CO2Na and elemental sulfur
Zhai, Lijuan,Li, Yaming,Yin, Jun,Jin, Kun,Zhang, Rong,Fu, Xinmei,Duan, Chunying
, p. 10262 - 10266 (2013/11/19)
A practical three-component copper-mediated oxidative trifluoromethylthiolation of aryl boronic acids with cheap and readily available sodium trifluoroacetate and elemental sulfur is reported. A variety of trifluoromethylthio-substituted aromatics are synthesized in moderate yields under mild reaction conditions.
