Synthesis of phosphate stabilised iodanes and their application in intramolecular aryl migrations.

A diverse set of hydroxy-benzo[]iodadioxaphosphinine oxides and derived diaryl iodonium salts are prepared and two examples are characterized by X-ray crystallography, featuring an out-of-plane geometry of the hypervalent bond for both compound classes. Treatment of the phosphate-stabilized diaryliodonium salts with Ca(OH) results in an efficient base-induced intramolecular aryl migration under aqueous conditions, yielding iodo-substituted diaryl ethers with yields up to 94%. Our findings highlight the synthetic potential of this previously underexplored compound class in organic transformations.

Synthesis of -acyl carbazoles, phenoxazines and acridines from cyclic diaryliodonium salts.

-Acyl carbazoles can be efficiently produced through a single-step process using amides and cyclic diaryliodonium triflates. This convenient reaction is facilitated by copper iodide in -xylene, using the commonly found activating ligand diglyme. We have tested this method with a wide range of amides and iodonium triflates, proving its versatility with numerous substrates.

Synthesis and Single-Electron Oxidation of Bulky Bis(m-terphenyl)chalcogenides: The Quest for Kinetically Stabilized Radical Cations.

Sterically encumbered bis(m-terphenyl)chalcogenides, (2,6-Mes C H ) E (E=S, Se, Te) were obtained by the reaction of the chalcogen tetrafluorides, EF , with three equivalents of m-terphenyl lithium, 2,6-Mes C H Li. The single-electron oxidation of (2,6-Mes C H ) Te using XeF /K[B(C F ) ] afforded the radical cation [(2,6-Mes C H ) Te][B(C F ) ] that was isolated and fully characterized. The electrochemical oxidation of the lighter homologs (2,6-Mes C H ) E (E=S, Se) was irreversible and impaired by rapid decomposition.

One-Pot Synthesis of Heteroatom-Bridged Cyclic Diaryliodonium Salts.

Two one-pot procedures for the construction of - and -bridged diaryliodonium triflates are described. An effective aryne-mediated arylation of -iodophenols and -sulfonamides provides diarylether and diarylamine intermediates, which are subsequently oxidized and cyclized to the corresponding diaryliodaoxinium and -iodazinium salts. Different derivatizations were applied to demonstrate their capacity as useful building blocks and gain a deeper understanding toward the general reactivity of these underdeveloped but potentially highly useful compounds.

One-Pot Synthesis and Conformational Analysis of Six-Membered Cyclic Iodonium Salts.

Two one-pot procedures for the construction of carbon-bridged diaryliodonium triflates and tetrafluoroborates are described. Strong Brønsted acids enable the effective Friedel-Crafts alkylation with diversely substituted -iodobenzyl alcohol derivatives, providing diphenylmethane scaffolds, which are subsequently oxidized and cyclized to the corresponding dibenzo[,]iodininium salts. Based on NMR investigations and density functional theory (DFT) calculations, we could verify the so-far-undescribed existence of two stable isomers in cyclic iodonium salts substituted with aliphatic side chains in the carbon bridge.