CO2-activated NaClO-5H2O enabled smooth oxygen transfer to iodoarene: a highly practical synthesis of iodosylarene

Abstract

A safe, rapid, and environmentally friendly synthesis of iodosylarene (ArIO) has been developed using NaClO under a carbon dioxide (CO2) atmosphere. Exposure of iodoarene to NaClO-5H2O in acetonitrile under CO2 (1 atm) resulted in the clean formation of ArIO within 10 minutes in high yield. The absence of a base in this method enables the direct use of in-situ-generated iodosylarene not only for a variety of oxidative transformations (synthesis of sulfilimine, pentavalent bismuth, benzyne adduct, etc.), but also for the synthesis of iodonium ylide and imino-λ 3 -iodane in one pot.

Green and Efficient Protocols for the Synthesis of Sulfonyl Fluorides Using Potassium Fluoride as the Sole Fluorine Source

“…This green approach retains all the advantages of existing protocols while adding a practical setup with high sustainability, as NaOCl·5H 2 O is an environmentally benign oxidant, with its postoxidation product being table salt (NaCl) . Based on our earlier investigations and prior studies by Miyamato and Uchiyama, , the key role of CO 2 atmosphere in NaOCl oxidation reactions was demonstrated to suppress overoxidation and generate the active species (hypochlorous acid, HOCl) to afford the desired product within a few minutes. Hence, we conducted the reaction of disulfide 3a with NaOCl·5H 2 O in BTF under a CO 2 atmosphere in the presence of KF as a fluorine source.…”

Auxiliary strategy for the general and practical synthesis of diaryliodonium(III) salts with diverse organocarboxylate counterions

“…Iodosoarenes 5b – f can be easily obtained by treating (dichloroiodo)arenes [ 41 ] or (diacetoxyiodo)arenes [ 42 ] with sodium hydroxide, by oxidation of iodoarenes with NaClO·5H 2 O [ 43 ], or by electrolysis [ 44 ]. The reaction scope of iodosoarenes 5b – f was explored with benzoic acid ( 6a ) and 1,3,5-trimethoxybenzene ( Scheme 5B ).…”

In Situ Generation of N-Triflylimino-λ3-iodanes: Application to Imidation of Phosphines and Catalytic α-Amidation of 1,3-Dicarbonyl Compounds

“…Although ArINTf can also be prepared by the ligand exchange of ArIF 2 with TMS 2 NTf (TMS = Me 3 Si) or by the imido transfer reaction of ArBrNTf to aryl iodides, it is difficult to deal with moisture-sensitive TMS 2 NTf and to synthesize ArBrNTf which requires BrF 3 with a risk of explosion. Very recently, Uchiyama and Miyamoto’s group reported an imidation reaction of thioanisole using PhINTf generated in situ from PhIO and TfNH 2 , albeit only one example was demonstrated . Furthermore, since ArINTf is rarely used in the organic reactions even including Uchiyama and Miyamoto’s example, ,, its reactivities are of interest.…”

“…Very recently, Uchiyama and Miyamoto’s group reported an imidation reaction of thioanisole using PhINTf generated in situ from PhIO and TfNH 2 , albeit only one example was demonstrated . Furthermore, since ArINTf is rarely used in the organic reactions even including Uchiyama and Miyamoto’s example, ,, its reactivities are of interest. Herein, we report the additive-free and convenient preparation of ArINTf from ArIO and TfNH 2 , the imidation of phosphines, and the α-amidation of 1,3-dicarbonyl compounds using the in situ generated ArINTf.…”