Recent Advances in Transition-Metal-Free Late-Stage C-H and N-H Arylation of Heteroarenes Using Diaryliodonium Salts

Abstract

Transition-metal-free direct arylation of C-H or N-H bonds is one of the key emerging methodologies that is currently attracting tremendous attention. Diaryliodonium salts serve as a stepping stone on the way to alternative environmentally friendly and straightforward pathways for the construction of C-C and C-heteroatom bonds. In this review, we emphasize the recent synthetic advances of late-stage C(sp2)-N and C(sp2)-C(sp2) bond-forming reactions under metal-free conditions using diaryliodonium salts as arylating reagent and its applications to the synthesis of new arylated bioactive heterocyclic compounds.

Tandem cyclization/arylation of diaryliodoniums via in situ constructed benzoxazole as a directing group for atom-economical transformation

“…2 However, compared with the significant advances in diaryliodoniums as traditional single-arylation reagents, methods for harnessing both aryl groups of them are less exploited, and only a few examples have been reported. 3 The groups of Muniz 4 and Jiang 5 have separately reported the use of symmetrical diaryliodoniums to construct biaryls via a C–C or C–S–C connection. However, a challenge emerges when unsymmetrical diaryliodoniums are employed.…”

Recent Progress in Cyclic Aryliodonium Chemistry: Syntheses and Applications

“…Although acyclic aryliodoniums have made significant advancements as arylating agents to assemble different compounds, the concern associated with their arylation process is the iodoarenes that are produced along with the desired arylated products and are often discarded as waste, which is problematic and should be addressed in the context of atom economy (Scheme 2C). 1,63 Compared to acyclic aryliodoniums, cyclic aryliodoniums are more atom-economical because the generated iodoarene remains as one part of the arylated products, which have further elaborating potential (Scheme 2D). 31,64,65 Owing to the highly electron-deficient property and unique ring system, cyclic aryliodoniums can be naturally considered to build various polycyclic scaffolds.…”

Controlled Halogen-Bond-Involving Assembly of Double-σ-Hole-Donating Diaryliodonium Cations and Ditopic Arene Sulfonates

“…Diaryliodonium monosulfonates are among the most studied iodonium salts thanks to their easy preparation and considerable reactivity as arylating agents in organic synthesis. − Therefore, it is not surprising that a fairly large number (more than 40) of X-ray structures of diaryliodonium sulfonates were reported over the years. About half of these structures exhibit 0D-heterotetrameric motifs, − while only two structures display 1D-chain , architectures (Figure A,C).…”