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

Grollier, Kévin; Taponard, Alexis; Zordo-Banliat, Arnaud de; Magnier, Emmanuel; Billard, Thierry

doi:10.3762/bjoc.16.252

Cited by 13 publications

(12 citation statements)

References 50 publications

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“…Noteworthy, the electrochemical protocol affords similar yields than the previously reported approaches that require stoichiometric quantities of reducing or activating agents. [43][44][45][46][47][48][49][50] Comparable limitations are also observed with non-activated alkyl halides delivering low yields of the desired products.…”

Section: Resultsmentioning

confidence: 99%

“…Despite the excellent yields obtained, sensitivity of TDAE encouraged the authors to develop a complementary way to achieve a similar umpolung approach. Replacing TDAE with tetrabutylammonium iodide (TBAI) allowed the in‐situ formation of CF 3 SeI under non‐reductive conditions (Scheme 1B, d) [49] . The milder set of conditions afforded good to excellent yields with reactive electrophiles (benzylic, allylic or propargylic) but provided lower conversions with non‐activated substrates.…”

Section: Introductionmentioning

confidence: 99%

“…Replacing TDAE with tetrabutylammonium iodide (TBAI) allowed the in-situ formation of CF 3 SeI under non-reductive conditions (Scheme 1B, d). [49] The milder set of conditions afforded good to excellent yields with reactive electrophiles (benzylic, allylic or propargylic) but provided lower conversions with non-activated substrates. More recently, they also reported a metal-based reductive approach that employs iron powder to reduce the TsSeCF 3 reagent.…”

Section: Introductionmentioning

confidence: 99%

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Electrochemical Trifluoromethylselenolation of Activated Alkyl Halides

et al. 2022

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A practical electrochemical method for the generation of CF3Se− anion from a shelf‐stable reagent (TsSeCF3) is reported allowing the metal‐free trifluoromethylselenolation of activated alkyl halides. Trifluoromethylselenolated compounds have been obtained in modest to excellent yields under the optimized reaction conditions. Finally, cyclic voltammetric and 19F NMR studies are presented and allowed to gain insight into the reaction mechanism.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Electrochemical Trifluoromethylselenolation of Activated Alkyl Halides

et al. 2022

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“…Thereby, still using the umpolung strategy, Billard and co-workers developed the iodide-mediated trifluoromethylselenolation in non-reductive conditions (Scheme 35). [60] The reaction showed good results with activated electrophiles such as benzylic ( 49 Besides electrophilic and nucleophilic trifluoromethylselenolation, Studer and co-workers reported the desulfonylative trifluoromethylselenolation of alkyl allyl sulfones with TsSeCF 3 as the radical trifluoromethylselenolation reagent (Scheme 36). [61] The yields of the products were excellent.…”

Section: Nontransition Metal Catalyzed/mediated Trifluoromethylselenolationmentioning

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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“…Considering the air and moisture sensitivity of TDAE, Billard and coworkers proposed an alternative activation mode in the presence of iodides (Scheme 23, right). [61] Indeed, mixing their reagent with 1 equivalent of TBAI (tetra-n-butylammonium iodide) can afford ISeR F with an inverted polarity respect to the starting reagent. A second equivalent of TBAI delivers the corresponding ammonium fluoroalkylselenides, which underwent the subsequent nucleophilic substitution.…”

Section: So 2 -(Fluoroalkyl) Selenosulfonatesmentioning

confidence: 99%

Synthesis, Reactivity and Activation Modes of Fluoroalkyl Thiosulfonates and Selenosulfonates

Ghiazza

Billard

2021

Eur J Org Chem

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Reagent design is at the cornerstone of modern organofluorine chemistry. The past decades have seen the emergence of diverse families of reagents with the aim of introducing fluoroalkylthio or seleno groups in an efficient and selective way. Among them, highly versatile fluoroalkyl thiosulfonates and selenosulfonates are in the foreground of the recent developments. Their applicability is discussed in detail in this Minireview, with a specific focus on the reactivity and activation modes.

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

Cited by 13 publications

References 50 publications

Electrochemical Trifluoromethylselenolation of Activated Alkyl Halides

Electrochemical Trifluoromethylselenolation of Activated Alkyl Halides

Recent Advances in the Development of Direct Trifluoromethylselenolation Reagents and Methods

Synthesis, Reactivity and Activation Modes of Fluoroalkyl Thiosulfonates and Selenosulfonates

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