Preparation, X-ray Structure, and Oxidative Reactivity of N-(2-Iodylphenyl)tosylamides and 2-Iodylphenyl Tosylate: Iodylarenes Stabilized by Ortho-Substitution with a Sulfonyl Group

Abstract

New tosyl derivatives of 2-iodylaniline and 2-iodylphenol were prepared by the dimethyldioxirane oxidation of the corresponding 2-iodophenyltosylamides or 2-iodophenyl tosylate and isolated as stable, microcrystalline products. Single-crystal X-ray diffraction analysis of N-(2-iodylphenyl)-N,4-dimethylbenzenesulfonamide revealed pseudocyclic structure formed by intramolecular I...O interactions between the hypervalent iodine center and the sulfonyl oxygens in the tosyl group. This tosylamide has an excellent solubility in organic solvents and is a potentially useful hypervalent iodine oxidant.

Advances in Synthetic Applications of Hypervalent Iodine Compounds

“…Such pseudocyclic iodine­(V) compounds have a significantly better solubility in organic solvents because their polymeric nature is partially disrupted by the redirection of secondary bonding. , Protasiewicz and co-workers have first prepared a pseudocyclic iodylarene, 1-( t -butylsulfonyl)-2-iodylbenzene 517 (Figure ), and structurally characterized this compound by X-ray crystallography. , The crystal structure of 517 revealed a pseudooctahedral geometry at the iodine atom with I–O bond lengths in the iodyl group of 1.796 and 1.822 Å and the intramolecular distance of 2.693 Å between one of the sulfone oxygen atoms and the iodine center. Following this pioneering study, various types of pseudocyclic iodylarenes bearing ortho -substituent, such as ethers 518 , esters 519 , , amides 520 , phosphine oxide 521 , sulfonate ester 522 , sulfonamides 523 , , nitro 524 , and amino derivatives 525 , 526 , , have been prepared from the corresponding iodoarenes using suitable oxidants (Figure ).…”

“…The pseudocyclic iodylarenes are useful reagents due to their good solubility in organic solvents. In particular, the pseudocyclic iodine­(V) compounds can oxidize sulfides and alcohols to the corresponding sulfoxides and carbonyl compounds. ,,,,,, These oxidations proceed without overoxidation to carboxylic acids and sulfones.…”

Practical synthesis of indoles and benzofurans in water using a heterogeneous bimetallic catalyst

“…2-Iodoanilines 13–16 were prepared following a standard procedure [35] although only 13 was known at the time of our studies. The preparation of 3-iodo-2-aminopyridines proved to be much more complicated.…”

Halogens

“…72 These include the previously unknown m-oxo-[bis(acetoxy)iodo]benzene ( Fig. 75 These compounds bear pseudocyclic structures formed by intramolecular IÁ Á ÁO interactions between the iodine atom and a sulfonyl oxygen. 1(b)), where the polymer chains form a remarkable pseudo triple-helix supramolecular structure and a tetrameric phenyliodine(III) sulfate ( Fig.…”

“…Furthering investigations of iodinanes bearing interacting ortho substituents, two new N-(2-iodylphenyl)tosylamides and 2-iodylphenyl tosylate have also been prepared and structurally characterized. 75 These compounds bear pseudocyclic structures formed by intramolecular IÁ Á ÁO interactions between the iodine atom and a sulfonyl oxygen. Mono-and perfluoroaryliodine(III) compounds, (ArIX 2 , X = F, CN) are known to possess strong intermolecular contacts between iodine and fluorine or nitrogen respectively.…”