Novel Synthesis of 5-Phenyliodonium Triflate Substituted Uracil Nucleosides

Abstract

5-Phenyliodonium triflate substituted uracil nucleosides have been prepared by one step reaction of uracil nucleosides with (diacetoxyiodo)benzene-trifluoromethanesulfonic acid.

Diaryliodonium Salts: A Journey from Obscurity to Fame

“…[24] Substituted (diacetoxyiodo)arenes have also been used, which allows for a larger product scope. [25] This route has been used in the synthesis of uracil-based diaryliodonium salts [26] and TMS-substituted salts that are used as precursors for benzyne (see Section 3.5.2). [27] Arylstannanes are more reactive than the corresponding aryl silanes in reactions with iodine(III) compounds.…”

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

“…In a pilot experiment, using 1,3-dimethyluracil 1a as a substrate, we examined the synthesis of uracil-aryliodonium triflates bearing electron-donating or electron-withdrawing aryl moieties in order to determine the influence of the substituent on the benzene ring (Table 1). PIDA derivatives bearing different para-substituents 2a – e were first used for a protocol previously reported by Kim et al [18]. The reported triflate 3aa-OTf was produced in a seemingly good yield, and afterwards, the reaction was precipitated as fine white powder in diethyl ether.…”

“…In 1998, Kim et al reported the uracil-5-ylphenyliodonium(III) triflates (Figure 1, right) prepared by the reaction of 5-tributylstannylated uracils with aryl(cyano)iodonoium triflate. They also demonstrated the preparation of uracil-5-ylphenyliodonium(III) triflates via the reaction of unfunctionalized uracil with phenyliodine(III) diacetate (PIDA) in the presence of triflic acid, and applied it to the palladium-catalyzed alkenylations [18,19]. Recently, the Gaunt research team prepared heteroaryl-uracil-iodonium(III) triflates using m CPBA ( m -chloroperbenzoic acid) and triflic acid as an oxidant and counterion, respectively, and then utilized these synthesized salts for organocatalytic arylation of aldehydes [20].…”

“…Recently, the Gaunt research team prepared heteroaryl-uracil-iodonium(III) triflates using m CPBA ( m -chloroperbenzoic acid) and triflic acid as an oxidant and counterion, respectively, and then utilized these synthesized salts for organocatalytic arylation of aldehydes [20]. However, the isolation and application of uracil-iodonium(III) salts remained mostly limited to treating triflate ( − OTf) salts [18,19,20,21,22], and the relationship between their stability and the structural feature of uracil-iodonium(III) salts has still not been sufficiently explored. This is likely because of their hygroscopic characteristics causing gradual decomposition, as claimed in previous studies [20].…”

Diaryliodoniumsalze – aus dem Nichts ins Rampenlicht

“…[24] Substituierte (Diacetoxyiod)arene wurden ebenfalls eingesetzt, um ein breiteres Produktspektrum zu erhalten. [25] Die gleiche Route führte auch zur Synthese von Uracil-basierten [26] und TMS-substituierten Diaryliodonium-salzen, die als Benzin-Vorstufen Verwendung finden (siehe Abschnitt 3.5.2). [27] Arylstannane sind in Reaktionen mit Iod(III)-Verbindungen reaktiver als die entsprechenden Arylsilane.…”