Flow Synthesis of Iodonium Trifluoroacetates through Direct Oxidation of Iodoarenes by Oxone®

Abstract

Flow chemistry is considered to be a versatile and complementary methodology for the preparation of valuable organic compounds. We describe a straightforward approach for the synthesis of iodonium trifluoroacetates through the direct oxidation of iodoarenes in a simple flow reactor using an Oxone‐filled cartridge. Optimization has been carried out using the Nelder–Mead algorithm. The procedure allows a wide range of iodonium salts to be prepared from simple starting materials.

Diaryliodoniums Salts as Coupling Partners for Transition-Metal Catalyzed C- and N-Arylation of Heteroarenes

“…Diaryliodonium salts are air-and moisture-stable, non-toxic, easy to handle and commercially available or easy to prepare [1][2][3][4][5][6][7][8]. During the last decade, noteworthy improvement in the synthesis and use of diaryliodonium salts has been reported [9][10][11][12][13][14][15][16][17][18][19][20][21]. Owing to their electron-deficient nature at the iodine center and to the excellent leaving-group ability of the iodoarene, diaryliodonium salts are frequently employed as aromatic electrophiles in aryl transfer processes [22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38].…”

Copper‐Catalyzed Selective N‐Arylation of Oxadiazolones by Diaryliodonium Salts

“…[41][42][43][44][45][46] Also, the synthetic procedures for preparing diaryliodonium salts make available the versatile scope of these compounds with high yields from common laboratory reagents. [47][48][49][50][51][52][53][54] Nevertheless, the chemoselectivity of arylation of N,O-containing heterocycles presents a challenging task in hypervalent iodine chemistry. For instance, selective N-and O-arylation of pyridine-2-ones was problematic [58,59] until a recent report, where base-tuned chemoselectivity has been applied.…”

“…In the next stage, we changed the NaOH to the triethylamine, which allowed the isolation of target 3 in 83% yield ( The best result was achieved (Table 1, Entries 11 and 17) when 2 a or 2aBF 4 were used as the arylsource. In a further study, we used diaryliodonium triflates due to the convenience of its preparation using Oxone [53,54] or mCPBA [62,63] as oxidants.…”

Halogen Bonding Provides Heterooctameric Supramolecular Aggregation of Diaryliodonium Thiocyanate

“…Potassium thiocyanate was supplied by Reakhim (Moscow, Russia); methanol and acetone was supplied by Vekton (Saint Petersburg, Russia). [PhI(4-C 6 H 4 OMe)] (CF 3 CO 2 ) was prepared by the previously reported procedure [30]. The melting point was measured on a Stuart SMP30 apparatus (Cole-Parmer, Stone, Staffordshire, UK) in a capillary and is not corrected.…”

“…Crystals of diaryliodonium thiocyanate 1 were grown by cocrystallization of the equimolar amounts of 4-methoxyphenyl(phenyl)iodonium trifluoroacetate [30] and potassium thiocyanate KSCN in acetone upon slow evaporation at 20-25 • C.…”