Silver(I)-Catalyzed Iodination of Arenes: Tuning the Lewis Acidity of N-Iodosuccinimide Activation

Abstract

A mild and rapid method for the iodination of arenes that utilizes silver(I) triflimide as a catalyst for activation of N-iodosuccinimide has been developed. The transformation was found to be general for a wide range of anisole, aniline, acetanilide, and phenol derivatives and allowed the late-stage iodination of biologically active compounds such as PIMBA, a SPECT imaging agent of breast cancer, and (-)-IBZM, a dopamine D2 receptor antagonist. The method was also modified for the radioiodination of arenes using a one-pot procedure involving the in situ generation of [(125)I]-N-iodosuccinimide followed by the silver(I)-catalyzed iodination.

Rapid Iododeboronation with and without Gold Catalysis: Application to Radiolabelling of Arenes

“…Radioactive iodine is normally supplied in the form of NaI;t herefore, initial studies involved the iodination of 4-methoxybenzeneboronic acid (1b)w ith NIS, which was prepared in situ by pre-stirring NaI and N-chlorosuccinimide (NCS). [25] Under our standard gold-catalysed reaction conditions, the desired product 3b was formed in 80 %y ield. These general conditions were investigated for the radioiodination of boronic acid 1b,i nw hich radiochemical yields (RCY) were determined by radio-HPLCa nalysis of the crude product.…”

“…As our studies demonstrated that gold‐catalysed ipso ‐substitution of arylboronic acids by using NIS could be performed rapidly and efficiently under mild conditions, we were keen to investigate the application of this method into the radioiodination of arenes. Radioactive iodine is normally supplied in the form of NaI; therefore, initial studies involved the iodination of 4‐methoxybenzeneboronic acid ( 1 b ) with NIS, which was prepared in situ by pre‐stirring NaI and N ‐chlorosuccinimide (NCS) . Under our standard gold‐catalysed reaction conditions, the desired product 3 b was formed in 80 % yield.…”

Progress in the synthesis of perylene bisimide dyes

“…The reactions were carried out with a substantial loading of Ag(I) salt (80-90 mol%), which was required for an effective activation of NIS. 98 The presence of Cu(OAc) 2 was also indispensable to the positive reaction outcome. As reported by Glorius for reactions of heterocyclic compounds under similar conditions, the metal catalyst may play a dual role.…”

Convenient but powerful method to dope single-walled carbon nanotube films with iodonium salts

“…Recently, new reports about effective, mild and safe iodination procedures emerged for arenes (Espuña et al 2004;Barluenga et al 2007;Racys et al 2016) and heterocycles (Barluenga et al 1993;Hamri et al 2012;Przypis and Walczak 2019). In this subject, hypervalent iodine reagents have been at the forefront of synthetic methodology developments in the past 20 years (Merritt and Olofsson 2009;Yoshimura and Zhdankin 2016).…”

“…In this subject, hypervalent iodine reagents have been at the forefront of synthetic methodology developments in the past 20 years (Merritt and Olofsson 2009;Yoshimura and Zhdankin 2016). Multiple examples of iodonium salt usage in organic synthesis have been reported in recent literature (Barluenga et al 1993;Espuña et al 2004;Hamri et al 2012;Borzenko et al 2015;Racys et al 2016;Iskra and Murphree 2017;Liu et al 2017;Przypis and Walczak 2019). Aryliodonium and diaryliodonium salts play a special role in this field because they are air-and moisture stable and soluble in many organic solvents despite their reactive framework.…”