Nucleic acid related compounds. 118. Nonaqueous diazotization of aminopurine derivatives. Convenient access to 6-halo- and 2,6-dihalopurine nucleosides and 2'-deoxynucleosides with acyl or silyl halides.
Treatment of 9-(2,3,5-tri-O-acetyl-beta-d-ribofuranosyl)-2-amino-6-chloropurine (1) with TMS-Cl and benzyltriethylammonium nitrite (BTEA-NO2) in dichloromethane gave the crystalline 2,6-dichloropurine nucleoside 2, and acetyl chloride/BTEA-NO2 was equally effective ( approximately 85%, without chromatography). TMS-Br/tert-butyl nitrite/dibromomethane gave crystalline 2-bromo-6-chloro analogue 3 (85%). (Chloro or bromo)-dediazoniation of 3',5'-di-O-acetyl-2'-deoxyadenosine (4) gave the 6-[chloro (5, 63%) or bromo (6, 80%)]purine deoxynucleosides, and 2',3',5'-tri-O-acetyladenosine (8) was converted into the 6-chloropurine nucleoside 9 (71%).
Francom
Paula
P
Department of Chemistry and Biochemistry, Brigham Young University, Provo, Utah 84602-5700, USA.
Robins
Morris J
MJ
D002855:Chromatography, Thin Layer; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D009696:Nucleic Acids / Q000737:chemistry*; D011684:Purine Nucleosides / Q000032:analysis / Q000138:chemical synthesis* / Q000737:chemistry*
C474939:9-(2,3,5-tri-O-acetylribofuranosyl)-2-amino-6-chloropurine; D007202:Indicators and Reagents; D009696:Nucleic Acids; D011684:Purine Nucleosides