Synthesis of Uracil-Iodonium(III) Salts for Practical Utilization as Nucleobase Synthetic Modules

Abstract

Iodonium(III) salts bearing uracil moieties have recently appeared in the literature, but their structural scope and utilization are limited because of their hygroscopic characteristics. In this study, we describe our detailed investigations for synthesizing a series of uracil iodonium(III) salts derived with various structural motifs and counterions. These new compounds have been utilized as attractive synthetic modules in constructing functionalized nucleobase and nucleosides.

Diaryliodonium(iii) salts in one-pot double functionalization of C–IIIIandorthoC–H bonds

“…Hetaryne was also successfully generated by the C–H deprotonation of a diaryliodonium salt, leading to subsequent cycloaddition. 82 Dohi and Takenaga et al reported the first generation of uracilyne (a heteroaryne analog of uracil) via the deprotonation of uracil-iodonium tosylate (Scheme 45), which can be prepared from uracil via a simple condensation with a Koser-type reagent. Optimization of the reaction conditions indicated that the ortho -trifluoromethyl phenyl group was the most appropriate dummy aryl ligand for this transformation.…”

Heteroaryliodonium(III) Salts as Highly Reactive Electrophiles

“…Utilizing the unique character of the fluoroalcohol medium as a solvent, Kita et al developed a facile synthesis of heteroaryliodonium salts 24 and 25 through the condensation of thiophenes and pyrroles with an iodine(III) reagent, whereby trifluoroethanol (TFE) enhanced the efficiency of this type of condensation, significantly extending the product scope (Dohi et al, 2007(Dohi et al, , 2010Ito et al, 2010). Furthermore, this procedure could also be applied to the preparation of uracil-aryliodonium salts 26 possessing different types of aryl moieties and various counterions (Takenaga et al, 2018(Takenaga et al, , 2019a.…”

Catalytic and non-catalytic selective aryl transfer from (mesityl)iodonium(III) salts to diarylsulfide compounds

“…Recently, aiming at selective aryl transfer reactions, specific diaryliodonium(III) salts incorporating a non-transferable dummy group such as mesityl (Mes) [12][13][14] and an auxiliary 2,4,6-trimethoxyphenyl (TMP) [15][16][17][18][19] have been studied by scientists including our research group. In our continuous study of diaryliodonium(III) salts-mediated reactions, 20,21 we report herein diaryliodonium(III) triflates bearing a mesitylene (Mes) auxiliary to facilitate selective S-arylation of diarylsulfides to form triarylsulfonium triflates without the formation of Mes-derived byproduct salts (Scheme 2).…”