Recent advances in transition-metal-catalyzed incorporation of fluorine-containing groups

• Xiaowei Li,
• Xiaolin Shi,
• Xiangqian Li and
• Dayong Shi

Beilstein J. Org. Chem. 2019, 15, 2213–2270, doi:10.3762/bjoc.15.218

• way for late-stage modifications. In the same year, Yu’s group [122] reported a Pd(II)-catalyzed C–H trifluoromethylation of arenes with an electrophilic trifluoromethylation reagent using diverse heterocyclic directing groups. Notably, the presence of trifluoroacetic acid (TFA) is crucial for the Ar

One-pot sequential synthesis of tetrasubstituted thiophenes via sulfur ylide-like intermediates

• Jun Ki Kim,
• Hwan Jung Lim,
• Kyung Chae Jeong and
• Seong Jun Park

Beilstein J. Org. Chem. 2018, 14, 243–252, doi:10.3762/bjoc.14.16

• reactions involving sulfonium and sulfoxonium ylides have been reported recently [26][27][28][29][30][31][32]. For example, Shen and co-workers reported the use of trifluoromethyl-substituted sulfonium ylide 5 in electrophilic trifluoromethylation reactions [33][34]. Moreover, Maulide and co-workers

Progress in copper-catalyzed trifluoromethylation

• Guan-bao Li,
• Chao Zhang,
• Chun Song and
• Yu-dao Ma

Beilstein J. Org. Chem. 2018, 14, 155–181, doi:10.3762/bjoc.14.11

• generated trifluoromethyl anion and suppress its rapid decomposition (Scheme 2). S-(Trifluoromethyl)diphenylsulfonium salts, as commonly used electrophilic trifluoromethylation reagents, were orginally developed by the group of Yagupolskii [14]. When iodo-substituted aromatics and heteroaromatics were

• NMR spectroscopy and ESIMS. It was proposed that [CuCF3] was generated through reduction of S-(trifluoromethyl)diphenylsulfonium triflate by Cu0 through a single-electron transfer (SET) process (Scheme 3). In 2015, the group of Lu and Shen [16] developed a new electrophilic trifluoromethylation

• primary and secondary alkylboronic acids underwent the trifluoromethylation well under different optimized conditions. Trifluoromethylation of boronic acid derivatives with electrophilic trifluoromethylation reagents CF3+ reagents were also explored in the trifluoromethylation of boronic acid derivatives

One-pot three-component route for the synthesis of S-trifluoromethyl dithiocarbamates using Togni’s reagent

• Azim Ziyaei Halimehjani,
• Martin Dračínský and
• Petr Beier

Beilstein J. Org. Chem. 2017, 13, 2502–2508, doi:10.3762/bjoc.13.247

• rotation are in reasonable agreement with the experiments. Keywords: dithiocarbamates; electrophilic trifluoromethylation; Togni reagents; Introduction Dithiocarbamates are well known for their manifold applications as pesticides, fungicides and crop protection agents in agriculture [1][2][3], as

• been reported to introduce the trifluoromethyl group in organic structures including nucleophilic, electrophilic, radical and transition metal-mediated trifluoromethylations. Among the electrophilic trifluoromethylation methods, reagents based on hypervalent iodine (Togni's reagents I and II, Scheme 1b

Synthesis, characterization and initial evaluation of 5-nitro-1-(trifluoromethyl)-3H-1λ³,2-benziodaoxol-3-one

• Nico Santschi,
• Roman C. Sarott,
• Elisabeth Otth,
• Reinhard Kissner and
• Antonio Togni

Beilstein J. Org. Chem. 2014, 10, 1–6, doi:10.3762/bjoc.10.1

• trifluoromethylation; 19F NMR kinetics; nitration; organo-fluorine; Introduction Since the advent of the hypervalent-iodine-based electrophilic trifluoromethylation reagents 1 and 2 in 2006 they have found widespread application in organic synthesis (Figure 1) [1][2][3][4]. Recently, increasing interest has been

• kinetic studies showed that this new derivative is almost one order of magnitude more reactive. Furthermore, differential scanning calorimetry measurements indicated that, in addition, it is also safer to handle. Keywords: cyclic voltammetry; differential scanning calorimetry; electrophilic

Copper-catalyzed trifluoromethylation of alkenes with an electrophilic trifluoromethylating reagent

• Xiao-Ping Wang,
• Jin-Hong Lin,
• Cheng-Pan Zhang,
• Ji-Chang Xiao and
• Xing Zheng

Beilstein J. Org. Chem. 2013, 9, 2635–2640, doi:10.3762/bjoc.9.299

• electrophilic trifluoromethylation reagents can be considered as an oxidant. In the presence of base, both of the cation and Heck-type intermediates should be able to undergo hydrogen elimination to form a Cvinyl–CF3 bond. On the basis of these reports and our hypothesis, we commenced to examine the reaction of

• aromatic alkenes with electrophilic trifluoromethylation reagents in the presence of copper and base. Results and Discussion Previously, we reported that copper powder or cuprous iodide could promote trifluoromethylation of heteroaromatics, arylboronic acids or terminal alkynes with trifluoromethyl

• alkenes. Trifluoromethylation of 4-vinylbiphenyl by electrophilic trifluoromethylation reagents. Supporting Information Supporting Information File 404: Full experimental details, analytical data and spectra of the target compounds. Acknowledgements We thank the National Natural Science Foundation of

Shelf-stable electrophilic trifluoromethylating reagents: A brief historical perspective

• Norio Shibata,
• Andrej Matsnev and
• Dominique Cahard

Beilstein J. Org. Chem. 2010, 6, No. 65, doi:10.3762/bjoc.6.65

• -(trifluoromethyl)diarylsulfonium salts are effective for the electrophilic trifluoromethylation of thiophenolates. Since this pioneering work, the design and synthesis of electrophilic trifluoromethylating reagents have been extensively investigated. Historically, the chalcogenium salts developed by Umemoto and co

• trifluoromethylation of aliphatic alcohols and these are now commercially available. In 2008, we reported a novel fluorinated Johnson-type reagent for electrophilic trifluoromethylation of carbon-centered nucleophiles. This reagent has demonstrated high efficiency in trifluoromethylation of cyclic β-ketoesters and

• electrophilic trifluoromethylation by means of a diaryl(trifluoromethyl)sulfonium salt, Ar2S+CF3 SbF6− (3) [11]. This trifluoromethylating reagent was obtained by treatment of aryltrifluoromethyl sulfoxide 1 with SF3+ SbF6− and subsequent reaction of the fluoro(trifluoromethyl) arylsulfonium salt 2 with