Difluoroalkylation of Carbonyl Compounds with (1,1-Difluoroalkyl)silane Derivatives

Convenient Synthesis of Difluoromethyl Alcohols from Both Enolizable and Non‐Enolizable Carbonyl Compounds with Difluoromethyl Phenyl Sulfone

“…1 H NMR chemical shifts were determined relative to internal (CH 3 ) 4 Si (TMS) at δ = 0.0 ppm or to the signal of a residual protonated solvent: CDCl 3 δ = 7.26 ppm. 13 C NMR chemical shifts were determined relative to internal TMS at δ = 0.0 or to the 13 C signal of solvent: CDCl 3 δ = 77.0 ppm.…”

Functionalized fluoroalkyl and alkenyl silanes: Preparations, reactions, and synthetic applications

“…Both (difluoromethyl)trialkylsilanes (R3SiCF2H) [17] and bis(trimethylsilyl)difluoromethane [5] were found not to be general reagents for difluoromethylation. Meanwhile, difluoromethylation with difluoromethyl phenyl sulfone (PhSO 2 CHF 2 ) [18] is less effective for enolizable aldehydes and ketones.…”

“…1,1-Difluoroalkylsilanes and 1,1-difluoroethylsilane As discussed in Section 2.1, bromodifluoromethylsilane 2a undergoes three types of reaction with nucleophiles [3]. Under the silver ion catalysis, replacement of bromine with alkyl group occurs to provide difluoroalkylsilanes 138, which react with aldehydes (43-82%) and ketones (20-35%), respectively (Scheme 33) [17].…”

Fluoride ion-mediated nucleophilic fluoroalkylation of alkyl halides with Me3SiCF2SPh: Synthesis of PhSCF2- and CF2H-containing compounds

“…There are several methods for introducing the CF 2 H moiety [4,5,7,16], including (a) the deoxofluorination of aldehydes using SF 4 , DAST, or SeF 4 reagent [17,18], (b) nucleophilic fluorination of gem-bistriflates using TBAF [19], (c) fluorination of 1,2-or 1,3-dithianes using BrF 3 [12,20,21], (d) the addition of CBr 2 F 2 to double bonds [22], (e) S RN 1 reaction between a nucleophile and CHClF 2 [5,23], and (f) nucleophilic introduction of a CF 2 H moiety into carbonyl compounds using (difluoromethyl)dimethylphenylsilane [24] or difluoro[bis(trimethylsilyl)]methane [10]. More recently, both difluoromethyl phenyl sulfone (PhSO 2 CF 2 H) and [difluoro(phenylsulfonyl)-methyl]trimethylsilane (Me 3 SiCF 2 SO 2 Ph) were used as efficient nucleophilic difluoromethylating agents for a variety of electrophiles [25].…”