368-48-9Relevant articles and documents
Direct cupration of fluoroform
Zanardi, Alessandro,Novikov, Maxim A.,Martin, Eddy,Benet-Buchholz, Jordi,Grushin, Vladimir V.
, p. 20901 - 20913 (2011)
We have found the first reaction of direct cupration of fluoroform, the most attractive CF3 source for the introduction of the trifluoromethyl group into organic molecules. Treatment of CuX (X = Cl, Br, I) with 2 equiv of MOR (M = K, Na) in DMF or NMP produces novel alkoxycuprates that readily react with CF3H at room temperature and atmospheric pressure to give CuCF3 derivatives. The CuCl and t-BuOK (1:2) combination provides best results, furnishing the CuCF3 product within seconds in nearly quantitative yield. As demonstrated, neither CF3- nor CF2 mediate the Cu-CF3 bond formation, which accounts for its remarkably high selectivity. The fluoroform-derived CuCF3 solutions can be efficiently stabilized with TREAT HF to produce CuCF 3 reagents that readily trifluoromethylate organic and inorganic electrophiles in the absence of additional ligands such as phenanthroline. A series of novel Cu(I) complexes have been structurally characterized, including K(DMF)[Cu(OBu-t)2] (1), Na(DMF)2[Cu(OBu-t)2] (2), [K8Cu6(OBu-t)12(DMF)8(I)] + I- (3), and [Cu4(CF3) 2(C(OBu-t)2)2(μ3-OBu-t) 2] (7).
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Jarvie et al.
, p. 978 (1956)
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Mechanistic Insight into Copper-Mediated Trifluoromethylation of Aryl Halides: The Role of CuI
Jin, Yuxuan,Leng, Xuebing,Liu, He,Shen, Qilong,Wu, Jian
, p. 14367 - 14378 (2021/09/13)
The synthesis, characterization, and reactivity of key intermediates [Cu(CF3)(X)]-Q+ (X = CF3 or I, Q = PPh4) in copper-mediated trifluoromethylation of aryl halides were studied. Qualitative and quantitative studies showed [Cu(CF3)2]-Q+ and [Cu(CF3)(I)]-Q+ were not highly reactive. Instead, a much more reactive species, ligandless [CuCF3] or DMF-ligated species [(DMF)CuCF3], was generated in the presence of excess CuI. On the basis of these results, a general mechanistic map for CuI-promoted trifluoromethylation of aryl halides was proposed. Furthermore, on the basis of this mechanistic understanding, a HOAc-promoted protocol for trifluoromethylation of aryl halides with [Ph4P]+[Cu(CF3)2]- was developed.
Catalytic trifluoromethylation of iodoarenes by use of 2-trifluoromethylated benzimidazoline as trifluoromethylating reagent
Akiyama, Takahiko,Ishikawa, Taisuke,Kamiyama, Nanami,Uchikura, Tatsuhiro
supporting information, p. 2442 - 2447 (2020/11/07)
The trifluoromethylation of iodoarenes was accomplished by use of a 2-trifluoromethylbenzimidazoline derivative as the trifluoromethylating reagent and a catalytic amount of Cu(I) in the presence of 2,2'-bipyridyl as the ligand. Through a mechanistic study, we found that the oxidative addition of the iodoarene to the Cu(I)–CF3 species is the rate-determining step.
Silica-supported silver nanoparticles as an efficient catalyst for aromatic C-H alkylation and fluoroalkylation
Khrizanforov, Mikhail N.,Fedorenko, Svetlana V.,Mustafina, Asiya R.,Kholin, Kirill V.,Nizameev, Irek R.,Strekalova, Sofia O.,Grinenko, Valeriya V.,Gryaznova, Tatiana V.,Zairov, Rustem R.,Mazzaro, Raffaello,Morandi, Vittorio,Vomiero, Alberto,Budnikova, Yulia H.
supporting information, p. 9608 - 9616 (2018/08/06)
The efficient catalysis of oxidative alkylation and fluoroalkylation of aromatic C-H bonds is of paramount importance in the pharmaceutical and agrochemical industries, and requires the development of convenient Ag0-based nano-architectures with high catalytic activity and recyclability. We prepared Ag-doped silica nanoparticles (Ag0/+@SiO2) with a specific nano-architecture, where ultra-small sized silver cores are immersed in silica spheres, 40 nm in size. The nano-architecture provides an efficient electrochemical oxidation of Ag+@SiO2 without any external oxidant. In turn, Ag+@SiO2 5 mol% results in 100% conversion of arenes into their alkylated and fluoroalkylated derivatives in a single step at room temperature under nanoheterogeneous electrochemical conditions. Negligible oxidative leaching of silver from Ag0/+@SiO2 is recorded during the catalytic coupling of arenes with acetic, difluoroacetic and trifluoroacetic acids, which enables the good recyclability of the catalytic function of the Ag0/+@SiO2 nanostructure. The catalyst can be easily separated from the reaction mixture and reused a minimum of five times upon electrochemical regeneration. The use of the developed Ag0@SiO2 nano-architecture as a heterogeneous catalyst facilitates aromatic C-H bond substitution by alkyl and fluoroalkyl groups, which are privileged structural motifs in pharmaceuticals and agrochemicals.