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-Mes2C6H3)2E (E=S, Se, Te) were obtained by the reaction of the chalcogen tetrafluorides, EF4, with three equivalents of m-terphenyl lithium, 2,6-Mes2C6H3Li. The single-electron oxidation of (2,6-Mes2C6H3)2Te using XeF2/K[B(C6F5)4] afforded the radical cation [(2,6-Mes2C6H3)2Te][B(C6F5)4] that was isolated and fully characterized. The electrochemical oxidation of the lighter homologs (2,6-Mes2C6H3)2E (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 O- and N-bridged diaryliodonium triflates are described. An effective aryne-mediated arylation of o-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 towards the general reactivity of these underdeveloped but potentially highly useful compounds

One-Pot Synthesis and Conformational Analysis of 6-Membered Cyclic Iodonium Salts

In this article we describe an efficient approach for the synthesis of cyclic diaryliodonium salts. The method is based on benzyl alcohols as starting materials and consists of an Friedel-Crafts-arylation/oxidation sequence. Besides a deep optimization, particluar focusing on the choice and ratios of the utilized Bronsted-acids and oxidants, we explore the substrate scope of this transformation. We also discuss an interesting isomerism of cyclic iodonium salts substituted with aliphatic substituents at the bridge head carbon. <br /

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

N-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 p-xylene, using the commonly found activating ligand diglyme. We\u27ve tested this method with a wide range of amides and iodonium triflates, proving its versatility with numerous substrates. Beyond carbazoles, we also produced a variety of other N-heterocycles, such as acridines, phenoxazines, or phenazines, showcasing the robustness of our technique. In a broader sense, this new method creates two C-N bonds simultaneously based on a mono-halogenated starting material, thus allowing heterocycle formation with diminished halogen waste