Environmentally Compatible Access to α‐Trifluoromethylseleno‐Enones

Grollier, Kévin; Taponard, Alexis; Ghiazza, Clément; Magnier, Emmanuel; Billard, Thierry

doi:10.1002/hlca.202000185

Cited by 7 publications

(7 citation statements)

References 69 publications

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“…This reagent could also be applied for the synthesis of trifluoromethylselenolated carbonyl compounds through a Morita‐Baylis‐Hillman type reaction. Both acyclic and cyclic enones were compatible with this reaction (Scheme 33b) [58] . Of note, this transformation is very sensitive to steric hindrance, leading to a significant decrease in yields.…”

Section: Electrophilic Trifluoromethylselenolation Reagentsmentioning

confidence: 77%

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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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Section: Electrophilic Trifluoromethylselenolation Reagentsmentioning

confidence: 77%

“…Both acyclic and cyclic enones were compatible with this reaction (Scheme 33b). [58] Of note, this transformation is very sensitive to steric hindrance, leading to a significant decrease in yields.…”

Section: Nontransition Metal Catalyzed/mediated Trifluoromethylselenomentioning

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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“…Few years later, Billard and coworkers evaluated the reactivity of α,β-unsaturated carbonyl groups under Morita-Baylis-Hillman type conditions (Scheme 19B). [51] A simple and environmentally benign protocol was disclosed to activate the enones via the 1,4-attack of an oxygenated nucleophile (resulting from the deprotonation of either water or ethanol). Despite a promising efficiency with cyclic or acyclic unsaturated ketones or aldehyde, the reaction is very sensitive to steric hindrance resulting in a significant decrease of the yields.…”

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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“…Few years later, Billard and coworkers evaluated the reactivity of a,b-unsaturated carbonyl groups under Morita-Baylis-Hillman type conditions (Scheme 19, B). [51] A simple and environmentally benign protocol was disclosed to activate the enones via the 1,4-attack of an oxygenated nucleophile (resulting from the deprotonation of either water or ethanol). Despite a promising efficiency with cyclic or acyclic unsaturated ketones or aldehyde, the reaction is very sensitive to steric hindrance resulting in a significant decrease of the yields.…”

Section: Se-(fluoroalkyl) Arylselenosulfonatesmentioning

confidence: 99%

Front Cover: Synthesis, Reactivity and Activation Modes of Fluoroalkyl Thiosulfonates and Selenosulfonates (Eur. J. Org. Chem. 41/2021)

Ghiazza

Billard

2021

Eur J Org Chem

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The Front Cover shows highly versatile reagents gravitating in the galaxy of reactions aiming to introduce fluorine‐containing units, namely fluoroalkylchalcogenosulfonates. Indeed, this family of compounds enables trifluoromethylation, trifluoromethylsulfonylation, fluoroalkylthiolation, and fluoroalkylselenolation reactions through several activation modes. Thus, these valuable fluorinated motifs can be introduced following electrophilic, nucleophilic, or radical pathways onto a plethora of organic substrates. More information can be found in the Minireview by C. Ghiazza and T. Billard.

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Environmentally Compatible Access to α‐Trifluoromethylseleno‐Enones

Cited by 7 publications

References 69 publications

Recent Advances in the Development of Direct Trifluoromethylselenolation Reagents and Methods

Recent Advances in the Development of Direct Trifluoromethylselenolation Reagents and Methods

Synthesis, Reactivity and Activation Modes of Fluoroalkyl Thiosulfonates and Selenosulfonates

Front Cover: Synthesis, Reactivity and Activation Modes of Fluoroalkyl Thiosulfonates and Selenosulfonates (Eur. J. Org. Chem. 41/2021)

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