Visible-light mediated carbonyl trifluoromethylative amination as a practical method for the synthesis of β-trifluoromethyl tertiary alkylamines

Abstract

An operationally straightforward, visible-light-mediated multicomponent strategy for the construction of β-trifluoromethylated tertiary alkylamines from aldehydes, secondary amines and a convenient source of trifluoromethyl iodide is reported.

Applications of Halogen-Atom Transfer (XAT) for the Generation of Carbon Radicals in Synthetic Photochemistry and Photocatalysis

“…More recently, α-aminoalkyl radical-mediated XAT has also been proposed as part of an ATRA-type addition of CF 3 −I to enamines for the preparation of β-CF 3 alkylamines (Scheme 107). 512 In this case, the condensation of a secondary amine with an enolizable aldehyde led to the corresponding enamine 164 that was intercepted by the electrophilic F 3 C•. This polarized radical addition 29,513 provided the α-aminoalkyl radical 165 that was proposed to regenerate the F 3 C• by XAT with CF 3 −I.…”

Multicomponent reactions and photo/electrochemistry join forces: atom economy meets energy efficiency

“…In this case, they exploited the polarity match between an electrophilic trifluoromethyl radical and an in situ formed enamine (through condensation of secondary alkylamines and aliphatic aldehydes). 224 The absence of a photocatalyst was justified by the fact that enamines become potent reductants upon excitation with visible light, but an EDA complex between enamine and CF 3 I can be formed as well. Homolytic cleavage of CF 3 I is the first step for the generation of a trifluoromethyl radical that can attack the enamine.…”

Visible‐Light Promoted Radical Fluoroalkylation of O‐ and N‐Substituted Alkenes

“…However, if the secondary amine is taken in stoichiometric quantities and water is removed, the iminium ion is the main product. This scenario was realized by performing the reaction in the presence of molecular sieves [94] (Scheme 34). Fluoroalkylation was carried out using iodotrifluoromethane complexed with DMSO under CFL irradiation.…”