Copper-mediated arylsulfanylations and arylselanylations of pyrimidine or 7-deazapurine nucleosides and nucleotides

Abstract

The syntheses of 5-arylsulfanyl- or 5-arylselanylpyrimidine and 7-arylsulfanyl- or 7-arylselanyl-7-deazapurine nucleosides and nucleotides were developed by the Cu-mediated sulfanylations or selanylations of the corresponding 5-iodopyrimidine or 7-iodo-7-deazapurine nucleosides or nucleotides with diaryldisulfides or -diselenides. The reactions were also applicable for direct modifications of 2'-deoxycytidine triphosphate and the resulting 5-arylsulfanyl or 5-arylselanyl-dCTP served as substrates for the polymerase synthesis of modified DNA bearing arylsulfanyl or arylselanyl groups in the major groove.

Silver-catalyzed three-component reaction of uracils, arylboronic acids, and selenium: synthesis of 5-arylselanyluracils

“…Selenide 7 was detected by GC-MS when phenylboronic acid 2a was reacted with Se powder and diphenylethylene under the standard conditions [eqn (4)]; 7 was also formed when 6 was reacted with diphenylethylene [eqn (5)]. Moreover, the reaction of phenylboronic acid with diphenylethylene gave triphenylethylene 8 in 30% yield [eqn (6)]. These results suggest that phenylselanyl and phenyl radicals are generated in this reaction system.…”

“…Conversions from 5-halouracil include nucleophilic substitution reaction with phenylselenol promoted by microwave irradiation 5 and Cu-mediated cross-coupling reaction with a diaryl diselenide. 6 A more versatile method involves the reaction of 5-unsubstituted uracils with phenylselanyl chloride or a diaryl diselenide. Anzai reported the first synthesis of 5-phenylselanyluracil by reacting uracil with phenylselanyl chloride, 7 while Kim et al developed the reaction of a 5-unsubstituted uracil with phenylselanyl chloride in the presence of a silver reagent, such as Ag 2 O, AgBF 4 , or AgOCOCF 3 .…”

Transition-Metal-Catalyzed C–S, C–Se, and C–Te Bond Formations via Cross-Coupling and Atom-Economic Addition Reactions. Achievements and Challenges

“…353 Arylsulfanylation and arylselanylation of iodine derivatives of pyrimidine and 7-deazapurine nucleosides and nucleotides, mediated by CuI/bpy, for example, under the action of disulfides and diselenides, were described (Scheme 70, G). 354 Symmetrical and unsymmetrical diaryl sulfides are produced in good yields under optimized conditions in the reaction of aryl iodides with diaryl(dialkyl)disulfides and diaryldiselenides in DMSO under catalysis by CuI with 4′-(4-methoxyphenyl) 2,2′:6′,2″-terpyridine (Mtpy) at 110 °C (Scheme 70, H). 355 However, the yields drop upon using aryl bromides and aryl chlorides.…”

“…An interesting copper-promoted reaction of disulfide with thiophenols leading to the formation of a mixed sulfide is demonstrated by the example of 1,2-di­(pyrimidin-2-yl)­disulfides (Scheme , F) . Arylsulfanylation and arylselanylation of iodine derivatives of pyrimidine and 7-deazapurine nucleosides and nucleotides, mediated by CuI/bpy, for example, under the action of disulfides and diselenides, were described (Scheme , G) …”

General, Mild, and Metal‐Free Functionalization of Indole and Its Derivatives Through Direct C3‐Selenylation

“…alkyl halides) to form indoyl selenoethers . Finally, metal‐catalyzed indole and 5‐deazapurine selenylation reactions were reported, although harsh conditions of the processes (temperature ≈ 110 °C) limit their application in the synthesis …”