Recent advances in aza Friedel–Crafts reaction: strategies for achiral and stereoselective synthesis

Abstract

The aza-Friedel-Crafts Reaction is a very powerful tool to form C-C and C-N bonds, based on an acid-catalyzed addition of electron-rich aromatic compounds to imines. The stereoselective addition of a...

Chiral phosphoric acid-catalyzed enantioselective synthesis of functionalized pyrrolinones containing a geminal diamine core via an aza-Friedel–Crafts reaction of newly developed pyrrolinone ketimines

“…The chiral phosphoric acid 10 -catalyzed aza-Friedel–Crafts reaction enables the efficient coupling of electron-rich aromatic systems with imines to incorporate aminoalkyl groups into the aromatic ring. 11 Similarly, the application of amidines in the aza-Friedel–Crafts reaction can materialize the construction of chiral geminal diamine. Based on our group's research foundation in asymmetric organic catalysis, 12 we attempted to achieve the synthesis of chiral 2-substituted-2-amino-1 H -pyrrol-3(2 H )-ones containing a geminal diamine group through an asymmetric aza-Friedel–Crafts reaction of pyrrolinone ketimines 1 with phenolic compounds under the catalysis of chiral phosphoric acid.…”

Aza-Achmatowicz rearrangement coupled with intermolecular aza-Friedel–Crafts enables total syntheses of uleine and aspidosperma alkaloids

“…[63][64][65][66][67][68][69][70][71][72] It was interestingly noted that the intermolecular reaction of indoles with piperidine derivatives was rst reported in 1955 but rarely explored for the total synthesis of aspidosperma (and uleine) alkaloids, [73][74][75] probably due to the instability and unavailability of functionalized 2-hydroxypiperidines. In this article, we report the development of an intermolecular aza-Friedel-Cras (iAFC) reaction [76][77][78] of indoles with functionalized 2-hydroxypiperidines, which can be readily available from aza-Achmatowicz rearrangement and thus enables collective total synthesis of aspidosperma and uleine alkaloids (Scheme 1c(iv)).…”

Electrophilic aromatic substitution in eutectic-type mixtures: from an old concept to new sustainable horizons

“…3 Although this reaction has been known for almost 150 years and has found many applications in industrial processes, new advancements are still being proposed. 4 The classical protocols, using stoichiometric amounts of strong acids and halogenated solvents, are far away from the current sustainability standards.…”