Photochemical Synthesis of 6-Aryluridines¹⁾

Practical synthesis of 6-aryluridines via palladium(II) acetate catalyzed Suzuki–Miyaura cross-coupling reaction

“…23e28 The introduction of aryl substituents at the C6-position of uridine was limited to the following two approaches with a restricted scope: (1) photochemical arylation of 6-iodouridines with arenes; 28 (2) Stille coupling reactions of 6-iodouridines with arylstannanes or 6-tributylstannyluridines with aryl halides. 24e27 The synthesis of 6-aryluridine derivatives via the widely-used SuzukieMiyaura reaction was only very recently reported by Van Calenbergh et al 23 In an effort to explore the chemical synthesis and biological significance of 6-substituted uridine derivatives, we embarked on an investigation of a general and practical synthesis of 6-aryluridines via the SuzukieMiyaura reaction.…”

Development of Diversified Methods for Chemical Modification of the 5,6-Double Bond of Uracil Derivatives Depending on Active Methylene Compounds

“…As noted earlier in the Introduction, not so many chemical modification methods at the 6-position of uracil derivatives are reported in the literature, including the formation of 6-cyanouracil derivatives due to the cine -substitution reaction as shown in Scheme 1 [ 28 , 30 , 31 , 32 ]. In other examples, Tanaka and Miyasaka et al reported the electrophilic functionalization at the 6-position of 2',3'-isopropylidene-5'-methoxymethyluridine via lithiation at the 6-position of the uracil ring [ 48 ], and the photochemically-induced nucleophilic substitution at the 6-position of 6-iodo-2'3'-isopropylidene-5'-methoxymethyl-uridine [ 49 ]. Needless to say, the normal nucleophilic substitution of the 6-halogenouracil derivatives under basic conditions has also been reported in the literature [ 50 ].…”