Electrophilic trifluoromethylselenolation of terminal alkynes with <i>Se</i>-(trifluoromethyl) 4-methylbenzenesulfonoselenoate

Ghiazza, Clément; Tlili, Anis; Billard, Thierry

doi:10.3762/bjoc.13.260

Cited by 32 publications

(9 citation statements)

References 62 publications

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“…[4e] More recently,w er eported the synthesis as well as use of new shelf-stable reagents for electrophilic trifluoromethylselenolation, namely trifluoromethyl tolueneselenosulfonates. [7] As part of our continuing interest in discovering and developing new synthetic methods,weturned our attention to studying the formation of C(sp 2 ) À SeCF 3 bonds using the above-mentioned compound. Regarding the state of the art, the use of nucleophilic ammonium trifluoromethylselenide is the most studied approach in conjunction with aryl halides under nickel [8] or palladium [9] catalysis.A rene diazonium salts [10] and arylboronic acids [7b, 11] have also been used as starting materials.F inally,d iscrete s-bonded copper-SeCF 3 complexes have been employed in stoichiometric fashion for the trifluoromethylselenolation of aryl iodides and activated bromides.…”

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confidence: 99%

Visible‐Light‐Mediated Metal‐Free Synthesis of Trifluoromethylselenolated Arenes

et al. 2018

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The first visible-light-mediated synthesis of trifluoromethylselenolated arenes under metal-free conditions is reported. The use of an organic photocatalyst enables the trifluoromethylselenolation of arene diazonium salts using the shelf-stable reagent trifluoromethyl tolueneselenosulfonate at room temperature. The reaction does not require the presence of any additives and shows high functional-group tolerance, covering a very broad range of starting materials. Mechanistic investigations, including EPR spectroscopy, luminescence investigations, and cyclic voltammetry allow rationalization of the reaction mechanism.

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Visible‐Light‐Mediated Metal‐Free Synthesis of Trifluoromethylselenolated Arenes

et al. 2018

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“…Interestingly, the addition of TsSeCF 3 to substrates with oxygen as the directing group was observed in moderate to good yields ( 45 a – 45 c ). It's worth noting that the regioselectivity was inverted when compared to the previously reported addition reactions [57,64] . In comparision, there was no addition reaction observed for substrates with nitrogen as the directing group.…”

Section: Electrophilic Trifluoromethylselenolation Reagentsmentioning

confidence: 74%

“…As an electrophilic trifluoromethylselenolation reagent, TsSeCF 3 could also be applied to the difuctionalization of terminal alkynes (Scheme 33a) [57] . Good regioselectivity and diastereoselectivity were observed for both terminal aryl and aliphatic alkynes, albeit the yields for aliphatic alkynes were much lower.…”

Section: Electrophilic Trifluoromethylselenolation Reagentsmentioning

confidence: 99%

Recent Advances in the Development of Direct Trifluoromethylselenolation Reagents and Methods

Wang

Zhang

et al. 2021

Adv Synth Catal

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The introduction of trifluoromethylchalcogen group (CF 3 O, CF 3 S and CF 3 Se) has attracted growing attention in the field of modern organofluorine chemistry. Compared with the CF 3 S and CF 3 O chemistry, methods for trifluoromethylselenolation are much less developed owing to the limited availability of CF 3 Se transfer reagents and synthetic methods. The CF 3 Se group introduces promising lipophilicity (Hansch-Leo parameter = 1.29) and strong electron-withdrawing effect (Hammett constants σ m = 0.44, σ p = 0.45) which are important parameters for the development of new pharmaceutically relevant compounds. Traditionally, the CF 3 Se compounds were synthesized by the nucleophilic trifluoromethylation of diselenides and selenocyanates, which suffered from harsh conditions and/or limited substrates scope. Compared with the indirect methods, the direct formation of CÀ SeCF 3 constitutes is a more efficient approach. In recent years, new reagents and methods were developed which enabled the incorporation of the trifluoromethylselenyl group directly under mild conditions, specifically in transition metal catalysis and photoredox catalysis. In this review, we will focus on direct trifluoromethylselenolation strategies based on the development of new trifluoromethylselenolation reagents and methods. 2.1. MÀ SeCF 3 (M=Hg, Cu, Ag) 2.2. [(bpy)CuSeCF 3 ] 2 2.3. (Me 4 N)SeCF 3 2.4. BTÀ SeCF 3 3. Electrophilic Trifluoromethylselenolation Reagents 3.1. In situ formed CF 3 SeCl from BnSeCF 3 + SO 2 Cl 2 3.2. TsSeCF 3 4. Miscellaneous 5. Conclusions

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“…Afterwards, we extended the methodology to alkynes (Scheme 8). Although we demonstrated earlier that terminal alkynes could reacts with reagent I yielding trifluoromethylselenylated vinyl sulfone in THF without the requirement of light irradiation, the reaction was not effective for internal alkynes and only marginal conversion was obtained with aliphatic ones [14] . Under white LED irradiation we could circumvent these limitations, as shown in scheme 7 and a variety of terminal and internal alkynes could be converted to their vinyl sulfones products in very good to excellent yields.…”

Section: Trifluromethylselenolation Of Alkenes and Alkynesmentioning

confidence: 86%

Forging C‐SeCF₃ Bonds with Trifluoromethyl Tolueneselenosulfonate under Visible‐Light

Louvel

Ghiazza

Debrauwer

et al. 2021

The Chemical Record

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This account highlights some of our recent work on photoinduced trifluoromethylselenolation reactions. This research program relies primarily on the design of a new key shelf‐stable selenating reagent that can be involved in various radical processes In particular, we demonstrated that trifluoromethylselenolation of arenes, alkenes, alkynes as well as aliphatic organic building blocks can be readily achieved under visible‐light irradiation. Mechanistic investigations based on 19F NMR studies, EPR spectroscopy, cyclic voltammetry and luminescence studies allowed us to shed the light on the different proposed mechanisms in the designed methodologies. The applicative potential of these strategies was further demonstrated through the synthesis of bioactive analogue containing SeCF3 motif.

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

Cited by 32 publications

References 62 publications

Visible‐Light‐Mediated Metal‐Free Synthesis of Trifluoromethylselenolated Arenes

Visible‐Light‐Mediated Metal‐Free Synthesis of Trifluoromethylselenolated Arenes

Recent Advances in the Development of Direct Trifluoromethylselenolation Reagents and Methods

Forging C‐SeCF₃ Bonds with Trifluoromethyl Tolueneselenosulfonate under Visible‐Light

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

Cited by 32 publications

References 62 publications

Visible‐Light‐Mediated Metal‐Free Synthesis of Trifluoromethylselenolated Arenes

Visible‐Light‐Mediated Metal‐Free Synthesis of Trifluoromethylselenolated Arenes

Recent Advances in the Development of Direct Trifluoromethylselenolation Reagents and Methods

Forging C‐SeCF3 Bonds with Trifluoromethyl Tolueneselenosulfonate under Visible‐Light

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Forging C‐SeCF₃ Bonds with Trifluoromethyl Tolueneselenosulfonate under Visible‐Light