Synthesis and Application of Cyclic Diaryliodonium Salts: A Platform for Bifunctionalization in a Single Step

Abstract

In recent years the chemistry of cyclic iodonium salts has experienced ever‐growing development. The advantages of using cyclic iodonium salts over acyclic iodonium salts are that the reactions between cyclic iodonium salts and various nucleophiles lead, under suitable reaction conditions, to dual arylations in a one‐pot manner and to the formation of new heterocycles. Variously functionalized thiophenes, carbazoles, fluorenes, phenanthrenes and triazolophenanthridines have been synthesized by utilizing cyclic diaryliodonium salts. Various new ladder‐type π‐conjugated systems have also been synthesized by employing cyclic iodonium salts. In this microreview, the recent advancements in the synthesis and application of cyclic diaryliodonium salts are discussed in a systematic and concise manner.

Enhanced Reactivity by Torsional Strain of Cyclic Diaryliodonium in Cu-Catalyzed Enantioselective Ring-Opening Reaction

“…Recently, copper-catalyzed aminations of diaryliodonium have emerged as important methods for the synthesis of aniline derivatives. [39][40][41][42][43][44][45] Diaryliodoniums act as powerful reagents for arylation of nucleophiles in both asymmetric and non-asymmetric reactions, most notably in contributions from the Gaunt group. [46][47][48][49][50][51][52][53] We reasoned that the ring-opening reaction of cyclic diaryl iodoniums would give atropisomeric aryl iodides, which represent an ideal class of precursors for the divergent synthesis of biaryl atropisomers (Scheme 1E).…”

Diaryliodoniums Salts as Coupling Partners for Transition-Metal Catalyzed C- and N-Arylation of Heteroarenes

“…During the last decade, noteworthy improvement in the synthesis and use of diaryliodonium salts has been reported [9][10][11][12][13][14][15][16][17][18][19][20][21]. Owing to their electron-deficient nature at the iodine center and to the excellent leaving-group ability of the iodoarene, diaryliodonium salts are frequently employed as aromatic electrophiles in aryl transfer processes [22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38]. Seminal contributions from the Pike, Olofsson, Kita and Stuart groups highlighted the efficiency and the selectivity of this aforementioned reaction.…”

Substrate or Solvent‐Controlled PdII‐Catalyzed Regioselective Arylation of Quinolin‐4(1H)‐ones Using Diaryliodonium Salts: Facile Access to Benzoxocine and Aaptamine Analogues

“…However, only limited approaches are available for the construction of medium‐sized heterocycles . In an effort to demonstrate atom‐economical uses of cyclic diaryliodonium salts, we extended this strategy to access oxocino‐fused quinoline derivative via sequential C–C and C–O bond formation. Reaction of quinolin‐4(1 H )‐one ( 6a ) with diphenyleneiodonium triflate 9a under standard conditions afforded oxocino[2,3,4‐ de ]quinoline ( 10a ) in 70 % yield along with minor amount (20 % yield) of 5‐(2'‐iodo‐[1,1'‐biphenyl]‐2‐yl)quinolin‐4(1 H )‐one ( 11a ) (Scheme ).…”