An approach to metal-assisted DNA base pairing: novel beta-C-nucleosides with a 2-aminophenol or a catechol as the nucleobase.
The metal-chelating beta-C-nucleoside having a phenylenediamine moiety as the nucleobase was previously found to form a stable 2:1 complex with a Pd(2+) ion in aqueous media, where hydrogen bonding is replaced by metal coordination in the base pairing, thereby creating a novel hybridization motif in duplex DNA. In this regard, we have further designed two types of artificial beta-C-nucleosides possessing a metal-chelating site (a 2-aminophenol or a catechol) as the nucleobase moiety. These artificial nucleosides are directed toward controlling the net charges of the metal-assisted base pairs. This paper describes convenient syntheses of the artificial nucleosides bearing a 2-aminophenol or a catechol moiety. Each nucleoside was directly synthesized through 2'-deoxy derivative via a Friedel-Crafts coupling reaction as the key step between the aromatic ring and ribose moiety, whereas the nucleoside having a phenylenediamine moiety was prepared in rather longer steps through an RNA type intermediate followed by the removal of 2'-hydroxyl group.
Tanaka
K
K
Department of Chemistry, Graduate School of Science, The University of Tokyo, Hongo, Bunkyo-ku, 113-0033, Tokyo, Japan.
Tasaka
M
M
Cao
H
H
Shionoya
M
M
D000627:Aminophenols / Q000138:chemical synthesis*; D002396:Catechols / Q000138:chemical synthesis*; D002614:Chelating Agents / Q000138:chemical synthesis; D009705:Nucleosides / Q000138:chemical synthesis*
D000627:Aminophenols; D002396:Catechols; D002614:Chelating Agents; D009705:Nucleosides; C027667:2-aminophenol; C034221:catechol