Cover Feature: Nickel‐Catalyzed Aminofluoroalkylation of Alkenes: Access to Difluoroalkylated N‐Containing Heterocyclic Compounds (Eur. J. Org. Chem. 1/2022)

Abstract

The Cover Feature shows the nickel‐catalyzed aminofluoroalkylative cyclization reaction with unactive alkenes and iododifluoromethyl ketones for the synthesis of difluoroalkyl cyclic amines. The stone in the picture represents the flask filled with two reaction substrates. The Ni sword is the catalyst used to activate and accelerate the reaction, delivering the target compounds difluoroalkyl cyclic amines. More information can be found in the Full Paper by J. Wu, F. Wu et al.

Co-Catalyzed atom transfer radical addition of bromodifluoroacetamides, expanding the scope of radical difluoroalkylation

“…Wu et al has quite recently reported the ATRA-type reaction of 2,2-difluoro-2-iodoacetophenones to N -(ω-alkenyl)anilines catalyzed by Ni(acac) 2 /phen in the presence of K 2 CO 3 in dioxane at 100 °C. 11 This nickel catalyst system was applied to the reaction of 1a and 2a . However, 3aa was not detected, and the starting materials were recovered unreacted.…”

Fluoroalkyl Iodides in Fluoroalkylative Difunctionalization of C−C Multiple Bonds

“…Similar transformations, proceeding under Pd‐catalysis were developed by Fuchikami in 1987 [156] . Recently, intramolecular aminofluoroalkylation of alkenes with iododifluoromethyl ketones was realized under nickel catalysis [157] . Depending on the length of the tether between amine and olefinic fragments aziridenes, pyrrolidines or piperidines were obtained in good yields.…”

Recent advances in the accessibility, synthetic utility, and biological applications of aziridines

“…9 Among them, nickel was employed and in 2022 Wu and co-workers reported a nickel-catalyzed aminofluoroalkylative cyclization of unactive alkenes (15) with iododifluoromethyl ketones (14) to afford versatile difluoroalkylated nitrogen-containing hetorocycles including aziridines (18), as shown in Scheme 4. 10 According to the authors, the transformation proceeds through a radical mechanism. Upon treatment with the Ni-catalyst and base, iododifluoromethyl ketones ( 14) are transformed into inter-Scheme 1 Flow BDMS generation/alkene sulfobromination/aziridination sequence.…”