Transition-metal-catalyzed C–H bond activation as a sustainable strategy for the synthesis of fluorinated molecules: an overview

• Louis Monsigny,
• Floriane Doche and
• Tatiana Besset

Beilstein J. Org. Chem. 2023, 19, 448–473, doi:10.3762/bjoc.19.35

• in the field have been interested in the design of original methodologies for the trifluoromethylthiolation and more recently the difluoromethylthiolation of various compounds by transition-metal catalysis [78]. Moreover, a recent interest was devoted to the trifluoromethylselenolation reaction as

• approach. Of high interest, the modularity of the SCF2CO2Et was highlighted by its conversion into various other fluorinated residues (amide, carboxylic acid) and its selective oxidation into the corresponding sulfoxide and sulfone. I.5) Trifluoromethylselenolation of aromatic and vinylic C(sp2)–H bonds by

• palladium catalysis Very recently, the palladium-catalyzed trifluoromethylselenolation of (hetero)aromatic and olefinic derivatives has been investigated by the group of Billard using similar catalytic systems as those depicted for the trifluoromethylthiolation reactions. Indeed, using amides 37 derived

Metal-free nucleophilic trifluoromethylselenolation via an iodide-mediated umpolung reactivity of trifluoromethylselenotoluenesulfonate

• Kevin Grollier,
• Alexis Taponard,
• Arnaud De Zordo-Banliat,
• Emmanuel Magnier and
• Thierry Billard

Beilstein J. Org. Chem. 2020, 16, 3032–3037, doi:10.3762/bjoc.16.252

• . Metal-free nucleophilic trifluoromethylselenolations have been then performed with this in situ-generated anion. Perfluoroalkylselenolations have also been described. Keywords: fluorine; nucleophilic substitution; perfluoroalkylselenolation; selenium; trifluoromethylselenolation; Introduction Because

• agrochemistry. Even if, to date, there are no CF3Se-containing pharmaceuticals registered [15], a recent work has demonstrated the promising development of trifluoromethylselenolated nonsteroidal anti-inflammatory drugs as potential anticancer drugs [34]. Over the last years, trifluoromethylselenolation

• concerning the direct nucleophilic trifluoromethylselenolation. The nucleophilic fluoroalkylselenolation of alkyl bromides. Yields were determined by 19F NMR spectroscopy with PhOCF3 as an internal standard and yields of isolated products are shown in parentheses. aWith 1 equiv of electrophile 2. bStarting

Copper-promoted/copper-catalyzed trifluoromethylselenolation reactions

• Clément Ghiazza and
• Anis Tlili

Beilstein J. Org. Chem. 2020, 16, 305–316, doi:10.3762/bjoc.16.30

• advances have been made in the field of trifluoromethylselenolations of organic compounds where copper catalysis played a crucial role. Recent developments in this field are highlighted in this minireview. Keywords: copper catalysis; fluorine; homogenous catalysis; trifluoromethylselenolation

• one of the most lipophilic fluorinated groups, and thus potentially increases the bioavailability of the targeted drugs [10]. The focus of this minireview is to highlight the efforts made to use copper reagents for the promotion of trifluoromethylselenolation reactions. Review Overview on copper

• -promoted and copper-catalyzed processes for the introduction of SeCF3 groups Copper(I) trifluoromethylselenolate complexes Copper(I) trifluoromethylselenolate was first prepared in 1985 by the group of Yagupolskii [12]. Then, CuSeCF3·DMF was tested in the trifluoromethylselenolation of (hetero)aryl iodides

Electrophilic trifluoromethylselenolation of terminal alkynes with Se-(trifluoromethyl) 4-methylbenzenesulfonoselenoate

• Clément Ghiazza,
• Anis Tlili and
• Thierry Billard

Beilstein J. Org. Chem. 2017, 13, 2626–2630, doi:10.3762/bjoc.13.260

• obtained compounds are valuable building blocks for further syntheses of fluoroalkylselenolated molecules. Keywords: alkynes; nucleophilic addition; perfluoroalkylselenolation; Se-(trifluoromethyl) 4-methylbenzenesulfonoselenoate; trifluoromethylselenolation; Introduction Over the last decades

• interesting alternatives in the modulation of properties for various applications. Despite such potential interest for CF3Se compounds, methods to their syntheses remain still limited [39]. Direct trifluoromethylselenolation reactions have recently gained renewed interest and mainly follow two strategies. The

• reagent at hand we envisaged the trifluoromethylselenolation of alkynes. To our delight, the addition of 1a to phenylacetylene (2a) at room temperature, without any other practical precautions, lead to the expected addition product 3a with good yield (Scheme 1). Subsequently, the reaction was extended to