Stereoselective Conversion of Sugar Derivatives into C-nucleosides

Abstract

A two-step process for the transformation of readily available carbohydrate derivatives into acyclic C-nucleosides is described. The carbohydrate undergoes a scission process that is followed by the addition of aryl ketone derivatives, allowing the introduction of a variety of aryl rings. The resulting acyclic C-nucleosides are transformed into 2-deoxy cyclic pyranosides in good yield and excellent stereoselectivity.

C-Glycopyranosyl Arenes and Hetarenes: Synthetic Methods and Bioactivity Focused on Antidiabetic Potential

“…Another strategy exploited the diol 170, which, in an appropriate solvent and at low temperature, cyclized stereoselectively upon Lewis-acid activation to deliver C-2deoxy-glycosyl arenes 171 again in high yields. 201 In a different route, the Wittig−Horner adduct 172 easily cyclized in the presence of NIS 202 204 These ring-closure methods appear to be powerful tools for preparing elaborated carbohydrate derivatives. Most probably, this field will develop further, as suggested by a recent de novo approach to carbohydrates in which the acyclic precursors were obtained by tandem α-chlorination-aldol reactions with dynamic kinetic resolution.…”

“…The hemiketals (like 168 ) formed primarily were converted in acidic methanol to the methyl glycoside 166 or reduced stereoselectively to afford C -2-deoxy-glycosyl arenes 169 , respectively. Another strategy exploited the diol 170 , which, in an appropriate solvent and at low temperature, cyclized stereoselectively upon Lewis-acid activation to deliver C -2-deoxy-glycosyl arenes 171 again in high yields …”

“Cut and Paste” Processes in the Search of Bioactive Products: One-Pot, Metal-free O-Radical Scission-Oxidation-Addition of C, N or P-Nucleophiles

“…When the substrates are aminoacids or β-hydroxyamines, an intermediate iminium ion is formed, while carbohydrate substrates afford oxycarbenium ion intermediates. These cationic species may then undergo nucleophilic addition; most reports describe the addition of oxygen nucleophiles ( Chai et al, 1998a ; 2005 ; Francisco et al, 2001 ; Boto et al, 2005a ; 2007a ; 2008a ; Miguélez et al, 2012 ; Kiyokawa et al, 2018 ), but this minireview will focus on carbon, nitrogen and phosphorous nucleophiles. Since several transformations are carried out consecutively, with no need to purify the intermediates, these one-pot radical-polar crossover reactions save time, materials and energy with respect to the original conditions.…”

Synthesis and cytotoxic evaluation of apioarabinofuranosyl pyrimidines

“…Modified nucleosides constitute a vast and diverse family of biologically active compounds (Jordheim, Durantel, Zoulim, & Dumontet, ; Mehellou & De Clercq, ; Shelton et al, ) due to their bioisosterism with the natural derivatives have always attracted the interest among synthetic medicinal chemists toward antiviral and anticancer therapeutic research (Lak et al, ; Panayides et al, ; Parker, ; Pradere et al, ). In this regard, different structural modifications have been reported (Amblard, Cho, & Schinazi, ; Blade et al, ; Borland et al, ;Flores et al, ; Legrave et al, ; Liang, Pitteloud, & Wnuk, ; Miguélez, Batchu, & Boto, ; Rao, Manmode, & Hotha, ; Romeo et al, ) in both the sugar ring as well as the nucleobase. Among the different classes of modified nucleosides, arabino configuration and its bioisosteric analogues also showed good anticancer and antiviral activities.…”