Scalable electrochemical synthesis of diaryliodonium salts

Abstract

The synthesis of cyclic and acyclic diaryliodonium salts by anodic oxidation of iodobiaryls and iodoarene/arene mixtures has been developed in a simple undivided electrolysis cell in MeCN–HFIP–TfOH without any added electrolyte salts.

Updates on hypervalent-iodine reagents: metal-free functionalisation of alkenes, alkynes and heterocycles

“…The reaction is oxidant free and hence generates no chemical waste (Scheme 4). 49 The trifluoromethanesulfonic acid mediated synthesis of pseudocyclic β-trifluorosulfonyloxy vinylbenziodoxolones (VBXs) (8) was reported by the Yoshimura group using alkynes (7) and hydroxybenziodoxolones. The reaction of the synthesised VBXs with sodium azide leads to the formation of β-azido vinylbenziodoxolones (8) via the vinylic nucleophilic substitution reaction with the retention of the configuration of the double bond (Scheme 5).…”

“…Next, the azidyl radical attacks the double bond of Oxazolidinone antibiotics are mainly employed in the treatment of drug-resistant bacterial infections, especially tuberculosis which increases their synthetic demand. 88 In 2021, the Moran group developed an HVI mediated synthesis of oxazolidinones (50) via cyclisation of allyl carbamates (49). A wide variety of allyl carbamates were converted to substituted oxazolidinones.…”

Recent Updates on Electrogenerated Hypervalent Iodine Derivatives and Their Applications as Mediators in Organic Electrosynthesis

“…Almost at the same time, Moran and co-workers also established an electrochemical approach to synthesis cyclic and acyclic diaryliodonium salts 9 ( Elsherbini and Moran, 2021 ). In a simple undivided electrolysis cell in MeCN-HFIP-TfOH without any added electrolyte salts, more than 30 diaryliodonium salts 9 were achieved in high to excellent yields via anodic oxidation of iodobiaryls and iodoarene/arene ( Scheme 1E ).…”

Two-step continuous-flow synthesis of 6-membered cyclic iodonium salts via anodic oxidation

“…Nonetheless, HVIs, DIS and CDIS have been generated by anodic oxidation [37][38][39][40]. Due to the apparent advantages of electrochemical processes, their implementation in flow is simple and straightforward since further dilution or additives are unnecessary [41,42].…”