Synthetic Approaches to Trifluoromethylselenolated Compounds

Tlili, Anis; Ismalaj, Ermal; Glenadel, Quentin; Ghiazza, Clément; Billard, Thierry

doi:10.1002/chem.201704637

Cited by 85 publications

(42 citation statements)

References 81 publications

(90 reference statements)

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“…In recent years, the latestage and selective fluorination reaction of organic molecules has received significant attention, especially the trifluoromethoxylation reaction, which is one of the most important research hotspots, as the trifluoromethoxy group's electron-withdrawing effects and high lipophilicity (Hansch parameter π x = 1.04) [6][7][8][9][10] . However, the trifluoromethoxylation reaction remain limitations and challenges, such as limited trifluoromethoxylation reagents and instability of trifluoromethoxide anion, which impede its development and application [11][12][13][14] .…”

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confidence: 99%

Nucleophilic trifluoromethoxylation of alkyl halides without silver

Yang

Xin

et al. 2020

Nat Commun

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The biological properties of molecules containing the trifluoromethoxy group have made these compounds important targets in pharmaceuticals and agrochemicals, yet their preparation is still a substantial challenge. Herein, we present a practical nucleophilic trifluoromethoxylation of alkyl halides with (E)-O-trifluoromethyl-benzaldoximes (TFBO) as a trifluoromethoxylation reagent in the absence of silver under mild reaction conditions. The trifluoromethoxylation reagent TFBO is easily prepared and thermally stable, and can release CF 3 O − species in the presence of a base. Furthermore, broad scope and good functional group compatibility are demonstrated by application of the method to the late-stage trifluoromethoxylation of alkyl halides in complex small molecules.

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confidence: 99%

Nucleophilic trifluoromethoxylation of alkyl halides without silver

Yang

Xin

et al. 2020

Nat Commun

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“…[17] With aH ansch parameter (p)o f1 .29 [18] and Hammett constants s m and s p of 0.44 and 0.45, [19] respectively, the SeCF 3 group has lipophilic and electronic properties between those of SCF 3 and OCF 3 and could thus allow for better fine tuning of am olecule's properties. Selenium derivatives are attracting increasing interestf or applications in materials and medicinal chemistry.…”

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confidence: 99%

Deoxytrifluoromethylthiolation and Selenylation of Alcohols by Using Benzothiazolium Reagents

Dix

Jakob

Hopkinson

2019

Chemistry A European J

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Aliphatic compounds substituted with medicinally importantt rifluoromethylthio (SCF 3 )a nd trifluoromethylselenyl (SeCF 3 )g roups weres ynthesized directly from alcohols by using the new benzothiazolium salts BT-SCF 3 and BT-SeCF 3 .T hese bench-stable fluorine-containing reagents are facile to use and can be prepared in two steps from non-fluorinated heteroaromatic startingm aterials. The metal-free deoxytrifluoromethylthiolation process using BT-SCF 3 proceeds under mild conditions and the similarly efficient trifluoromethylselenylationr eactions using BT-SeCF 3 are, to the besto fo ur knowledge, the first reported examples of this transformation.Scheme1.a) Benzothiazolium Reagents BT-SCF 3 and BT-SeCF 3 .b )Previously reported deoxytrifluoromethylthiolation reactionso fa liphatic alcohols. c) This work: Deoxytrifluoromethylthiolation and selenylation of alcohols with BT-SCF 3 and BT-SeCF 3 .[bmim] = 1-Butyl-3-methylimidazolium.[a] S.Scheme2.a) Two-step synthesisofBT-SCF 3 and its applicationi nthe deoxytrifluoromethylthiolation of aliphatic alcohol 2a.b)Likely reaction mechanism via 2-alkoxybenzothiazolium salt 4.

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“…[3a,4] Although only little information is available related to the physicochemical properties of SeCF 3 -containing molecules, the SeCF 3 motif is by far one of the most lipophilic fluorinated groups and would potentially increase the bioavailability of the targeted drugs. [98] Thus, methods for CÀ SeCF 3 bond formation have continuously been growing, which have attracted great interest in recent years. [98,99] This section highlights the efforts made to use hypervalent iodines as reliable oxidants for oxidative trifluoromethylselenolation with the nucleophilic SeCF 3 reagents under transitionmetal-mediated or -free conditions.…”

Section: Trifluoromethylselenolation Mediated By Hypervalent Iodine Rmentioning

confidence: 99%

Fluorination and Fluoroalkylation Reactions Mediated by Hypervalent Iodine Reagents

Han

Zhang

2020

Adv Synth Catal

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This review summarizes the progress in the fluorination and fluoroalkylation of electron-rich systems with diverse fluorine (F) and fluoroalkyl (R fn) reagents employing hypervalent iodine compounds as initiators in the last few decades. Because of the strong electrophilicity, high oxidizing properties, low toxicity, air and moisture stability, ready availability, ease of handling, and mild reaction conditions, the hypervalent iodine reagents have been widely utilized in modern organic chemistry. In particular, the use of hypervalent iodine reagents to initiate the CÀ F and CÀ R fn (R fn =CF 2 H, CF 3 , perfluoroalkyl, OCH 2 CF 3 , SCF 3 , SeCF 3 and etc) bond formation has been increasingly developed. In these reactions, hypervalent iodine compounds behave as powerful oxidants or electrophiles and activate the fluorination/fluoroalkylation reagents, the transitionmetal catalysts, or the substrates to in situ form electrophilic or radical intermediates, which subsequently participate in fluorination, difluoromethylation, trifluoromethylation, perfluoroalkylation, trifluoroethoxylation, fluoroalkylthiolation, trifluoromethylselenolation and others under mild conditions. Although great achievements have been made in this area, they are just the initial phase and still require a wide scope for improvement. It is anticipated that this review will draw much attention from the organic chemistry community and inspire more contributions in the development of new hyper-valent-iodine-mediated fluorination and fluoroalkylation reactions.

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Synthetic Approaches to Trifluoromethylselenolated Compounds

Cited by 85 publications

References 81 publications

Nucleophilic trifluoromethoxylation of alkyl halides without silver

Nucleophilic trifluoromethoxylation of alkyl halides without silver

Deoxytrifluoromethylthiolation and Selenylation of Alcohols by Using Benzothiazolium Reagents

Fluorination and Fluoroalkylation Reactions Mediated by Hypervalent Iodine Reagents

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