Review on UV-Induced Cationic Frontal Polymerization of Epoxy Monomers

Ultraviolet (UV)-induced cationic frontal polymerization has emerged as a novel technique that allows rapid curing of various epoxy monomers upon UV irradiation within a few seconds. In the presence of a diaryliodonium salt photoinitiator together with a thermal radical initiator, the cationic ring opening polymerization of an epoxide monomer is auto-accelerated in the form of a self-propagating front upon UV irradiation. This hot propagating front generates the required enthalpy to sustain curing reaction throughout the resin formulation without further need for UV irradiation. This unique reaction pathway makes the cationic frontal polymerization a promising route towards the efficient curing of epoxy-based thermosetting resins and related composite structures. This review represents a comprehensive overview of the mechanism and progress of UV-induced cationic frontal polymerization of epoxy monomers that have been reported so far in literature. At the same time, this review covers important aspects on the frontal polymerization of various epoxide monomers involving the chemistry of the initiators, the effect of appropriate sensitizers, diluents and fillers.

Oxidative alkylation of alkenes with carbonyl compounds through concomitant 1,2-aryl migration by photoredox catalysis

An efficient protocol for the construction of 1,5-diketones was realized in the presence of organic fluorophore 4CzIPN, diaryliodonium salt, and visible light irradiation.

Domino N-/C- or N-/N-/C-arylation of imidazoles to yield polyaryl imidazolium salts via atom-economical use of diaryliodonium salts

A Cu-mediated domino di-/triarylation reaction of imidazoles in a single step by using two aryls as well as an anion of a diaryliodonium salt is developed to quickly achieve polyaryl imidazolium salts.

Copper-Catalyzed Base-Free N-Arylation of 8-Aminoquinoline Amides through Chelation Assistance

A new and efficient approach for the N-arylation of 8-aminoquinoline amides with diaryliodonium salts has been developed. This chelation-assisted selective C–N cross-coupling reaction gave the desired N-arylated 8-aminoquinoline in moderate to good yields. In contrast to previous reports, no additional ligands and bases are used in this transformation. In addition, the anion of the diaryliodonium salt plays an important role in the success of the process.

Metal-free formal synthesis of phenoxazine

A transition metal-free formal synthesis of phenoxazine is presented. The key step of the sequence is a high-yielding O-arylation of a phenol with an unsymmetrical diaryliodonium salt to provide an ortho-disubstituted diaryl ether. This species was cyclized to acetylphenoxazine in moderate yield. The overall yield in the three-step sequence is 72% based on recovered diaryl ether. An interesting, unusually stable iodine(III) intermediate in the O-arylation was observed by NMR and could be converted to the product upon longer reaction time.