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

Abstract

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 o-iodobenzyl alcohol derivatives, providing diphenylmethane scaffolds, which are subsequently oxidized and cyclized to the corresponding dibenzo-[b,e]iodininium salts. Based on NMR investigations and density functional theory (DFT) calculations, we could verify the so-farundescribed existence of two stable isomers in cyclic iodonium salts substituted with aliphatic side chains in the carbon bridge. Article pubs.acs.org/joc

Zwitterionic iodonium species afford halogen bond-based porous organic frameworks

“…Iodonium salts 1–3 were synthesized oxidizing this compound with Oxone®/H 2 SO 4 (ref. 49 and 64–68) and coupling it with mesitylene, 1,4-dimethylbenzene, and chlorobenzene (Scheme 1 and Section S1†). On crystallization of 1 from MeOH : H 2 O mixtures, two different crystal forms 1a and 1b were obtained depending on the water content: 15 : 1 (v/v) afforded 1a , while methanol with >20% H 2 O afforded 1b .…”

Tuning the Halogen Bonding Strength of Cyclic Diaryliodonium Salts

“…The iodininium salt 2 was synthesized according to a literature procedure by Nachtsheim et al [40] . An interesting feature of this six‐membered core structure is the fact that it can also be modified on the bridging atom between the two aryl moieties.…”

Stabilization of Ethynyl-Substituted Aryl-λ3-Iodanes by Tethered N-Heterocylces

“…Initially, we were focused on the synthesis of pseudocyclic TIPS-ENHIs. Starting from our previous results for the synthesis of cyclic diaryliodonium salts using one-pot procedures, [21,22] we were intended to directly develop a convenient oxidation/alkynylation reaction. One-pot procedures for unsubstituted TIPS-ethynyl iodonium salts and EBX reagents have already been described, using meta-chloroperbenzoic acid (mCPBA) as the terminal oxidant in the presence of strong acids such as TfOH or TsOH and the subsequent addition of an alkyne to the in situ formed hydroxy(aryl)iodonium salt.…”