1,4-Addition of the CF3 group, perfluoroalkyl groups and functionalized difluoromethylated moieties: An overview

1,6-Nucleophilic Di- and Trifluoromethylation of para-Quinone Methides with Me3SiCF2H/Me3SiCF3 Facilitated by CsF/18-Crown-6

“…Due to the hard nature of fluoroalkyl anions, the direct regioselective 1,4-nucleophilic fluoroalkylation of α,β-unsaturated carbonyl compounds is a challenging task [ 38 , 39 , 40 , 41 ], and 1,4-nucleophilic fluoroalkylations are often accompanied with a 1,2-addition reaction [ 39 , 40 ]. Moreover, 1,4-trifluoromethylation of Me 3 SiCF 3 activated by AcONa or TBAF [ 38 ] is mainly limited to electron-deficient olefins containing two electron-withdrawing groups.…”

“…Due to the hard nature of fluoroalkyl anions, the direct regioselective 1,4-nucleophilic fluoroalkylation of α,β-unsaturated carbonyl compounds is a challenging task [ 38 , 39 , 40 , 41 ], and 1,4-nucleophilic fluoroalkylations are often accompanied with a 1,2-addition reaction [ 39 , 40 ]. Moreover, 1,4-trifluoromethylation of Me 3 SiCF 3 activated by AcONa or TBAF [ 38 ] is mainly limited to electron-deficient olefins containing two electron-withdrawing groups. However, weak basic initiators struggle to cleave the Si-CF 2 H bond of Me 3 SiCF 2 H, and using Me 3 SiCF 2 H to engage in 1,4-/1,6-nucleophilic addition of α,β-unsaturated carbonyl compounds is difficult and has not been reported previously.…”

Difluoromethylation Reactions of Organic Compounds

“…Difluoromethylation can also be accomplished through difluoromethyl reagents of the type Z‐CF 2 ‐Y (where Z,Y≠H, F), such as R 3 SiCF 2 COOEt, BrCF 2 COOEt, FSO 2 CF 2 COOH, TMSCF 2 SO 2 Ph, BrCF 2 SO 2 Ph, BrCF 2 P(O)OEt 2 , or ICF 2 SO 2 Ph . These reagents (Z−CF 2 Y, in which Z,Y≠H, F) append to organic molecules as CF 2 Y groups, and can ultimately be reduced to a CF 2 H motif .…”

“…A series of phosphonium difluoroalkyl sources such as Ph 3 P + CF 2 CO 2 − , (Me 2 N) 3 P + CF 2 CO 2 ‐ , have recently been shown to introduce a CF 2 Y moiety into alkenes, alkynes, phenols, thiols, carboxylic acids, and heterocyclic amines . These recently reviewed methods are not included in this review article. Unlike a thorough or exhaustive revision of the literature on difluoromethylation reactions, a discussion on the recent progress in the field and new reactions is intended, with a view towards future perspectives, outlining established methods for difluoromethylation of functional groups along with the recent developments (2015–present), which will include the late‐stage introduction of CF 2 H and CF 2 Y moieties into organic molecules.…”

Trifluoroethoxy-Coated Phthalocyanine Catalyzes Perfluoroalkylation of Alkenes under Visible-Light Irradiation

“…Perfluoroalkyl groups frequently appeared in the libraries of pharmaceuticals, agrochemicals, and functional materials and in the methods for the introduction of perfluoroalkyl groups to organic molecules, causing a massive accumulation of literature over the past few decades [ 1 , 2 , 3 , 4 , 5 ]. Radical perfluoroalkylation of alkenes using perfluoroalkyl halides (Rf-X) under shortwave UV irradiation is one of the classical and well-explored methods for this purpose [ 6 , 7 , 8 ].…”