Diaryliodonium Salts Enabled Arylation, Arylocyclization, and Aryl‐Migration

Abstract

Our research interest focusing on synthetic methodology with diaryliodonium salts, is summarized in this account. Besides employing a dual activation strategy of C−I and ortho C−H bonds, we have introduced vicinal functional groups at ortho‐positions of diaryliodonium salts, in which their unique reactivities have been explored in various processes, including arylation, diarylation, cascade annulation, benzocyclization, arylocyclization, and intramolecular aryl migration. The variety of mechanisms of these reactions that involves either transition metals, especially palladium in organometallic catalysis, or transition‐metal free conditions, were discussed in the context.

Gas-Phase Smiles Rearrangement of ortho-Nitro-substituted Diaryliodonium Cations and Their Mechanistic Insights

“…The preparation methods could be referred to relevant articles. [37][38][39] Some structures of the diaryliodonium salts (M ) were given in Scheme 2 , while the rest structures were shown in Scheme S1 , and they were labeled for convenience as 1 to 54 . Salts 24 , 33and 34 contained OTsas counter anion, the rest diaryliodonium salts contained OTfas counter anion.…”

Ortho-ester-substituted diaryliodonium salts enabled regioselective arylocyclization of naphthols toward 3,4-benzocoumarins

“…Diaryliodonium salts as electrophilic reagents have attracted significant attention in the field of organic synthesis owing to their efficiency and selectivity [1][2][3][4][5][6][7]. Particularly, they have been employed in benzocyclization and arylocyclization reactions, enabling intramolecular cyclization by forming aromatic or heterocyclic rings as a part of cyclic structures [8]. In these reactions, the dual activation of a C-I bond and vicinal C-H bonds/functional groups features a distinct advantage, facilitating the formation of two or more chemical bonds in a stepeconomic manner [9][10][11][12][13].…”

Palladium-Catalyzed Triple Suzuki–Miyaura Reactions Using Cyclic (Vinyl Triflate)iodonium Salts

“…Meanwhile, polyarylated ethylenes exhibit unique aggregation induced emission (AIE) effect, stemming from its unique molecular structure and optical properties . Recently, the exploration of diaryliodonium salts (Ar 2 IX) has witnessed notable advancement in facilitating arylocyclizations and polyarylations, significantly contributing to the development of synthetic methodologies for constructing these polyaromatic skeletons …”