title: Purinyl N1-directed aromatic C-H oxidation in 6-arylpurines and 6-arylpurine nucleosides.
abstract: Palladium-catalyzed C-H bond activation and oxidation of C6 arylpurines as well as C6 arylpurine nucleosides can be accomplished using Pd(OAc)2/PhI(OAc)2 in CH3CN. Despite the presence of four nitrogen atoms in the purine moiety as well as the polyoxygenated saccharide and a labile glycosidic bond in the nucleosides, these reactions can be effectively conducted. Notably, the generally more labile 2'-deoxyribonucleosides also undergo reaction. The reaction conditions can be tuned to yield either monoacetoxylated or diacetoxylated products predominantly. In the course of these investigations, a dimeric Pd(II)-containing cyclopalladated C6 naphthylpurine derivative has been obtained and crystallographically characterized. This compound is competent in catalyzing the oxidization with PhI(OAc)2, indicating its plausible intermediacy in the chemistry. The X-ray structure of a monoacetoxylated product from this reaction has also been obtained.
authors.affiliation: Department of Chemistry, The City College and The City University of New York, 160 Convent Avenue, New York, New York 10031, USA.
authors.forename: Raghu Ram
authors.initials: RR
authors.lastname: Chamala
authors.forename: Damon
authors.initials: D
authors.lastname: Parrish
authors.forename: Padmanava
authors.initials: P
authors.lastname: Pradhan
authors.forename: Mahesh K
authors.initials: MK
authors.lastname: Lakshman
mesh_terms: D019342:Acetic Acid / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D018360:Crystallography, X-Ray; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry; D010084:Oxidation-Reduction; D010165:Palladium / Q000737:chemistry; D011684:Purine Nucleosides / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D011684:Purine Nucleosides; D010165:Palladium; D019342:Acetic Acid