Copper‐Catalyzed Intermolecular Trifluoromethylazidation of Alkenes: Convenient Access to CF₃‐Containing Alkyl Azides

Abstract

A novel copper-catalyzed intermolecular trifluoromethylazidation of alkenes has been developed under mild reaction conditions. A variety of CF3 -containing organoazides were directly synthesized from a wide range of olefins, including activated and unactivated alkenes, and the resulting products can be easily transformed into the corresponding CF3 -containing amine derivatives.

Late Stage Azidation of Complex Molecules

“…43 Although this method has broad functional group tolerance, examples of trifluoromethylazidation were limited to substrates containing a single functional group and relatively simple natural products or their derivatives.…”

Direct Aromatic CH Trifluoromethylation via an Electron‐Donor–Acceptor Complex

“…There are three major ways to generate CF 3 . radical (Figure 1 a): i) oxidation of nucleophilic trifluoromethylating reagents, such as TMSCF 3 ,8a–c Langlois’s reagent (CF 3 SO 2 Na)8d–f and (CF 3 SO 2 ) 2 Zn;8g–h ii) reduction of electrophilic trifluoromethylating reagents, such as CF 3 SO 2 Cl,9a–b Umemoto’s reagent,9c–h Togni’s reagent9i–l and CF 3 I;9m–o iii) homolysis or mesolysis of trifluoromethyl halides 10. Recently, Melchiorre group reported photochemical aromatic perfluoroalkylation driven by the photochemically activated EDA complexes 4b.…”

Chromium(II)-catalyzed enantioselective arylation of ketones

“…Phenyl ketone 1d and ketones with electron-withdrawing groups in different substituent patterns gave the expected products with good enantiocontrol, while the enantioselectivity for ketone 1e bearing an electron-donating group decreased. The mild process exhibited excellent functional group tolerance, with chloride ( 2f ), fluoride ( 2g ), and CF 3 moieties ( 2h ) well tolerated for further manipulation [46–47]. Heteroaryl ketones such as furan-substituted ketone ( 1i ) were also suitable substrate, giving product 2i in 78% ee.…”