Synthesis of C-5 Substituted Tubercidin Derivatives.
Abstract
C-5 substituted pyrrolo(2,3-d)pyrimidine nucleosides are synthesized via reactions of 5-mercuritubercidin (2). Palladium catalyzed carbonylation of 2 in methanol gave 5-methoxycarbonyltubercidin (5) which could be converted to the nucleoside antibiotic sangivamycin (6) by reaction with ammonia. Reduction of 5 with LiBH4 in tetrahydrofuran gave 5-hydroxymethyltubercidin (7). Longer carbon chains were introduced by the palladium catalyzed coupling of olefins with mercuritubercidin. 5-Mercuritubercidin and methyl acrylate in 0.1 M Li2PdCl4 in methanol gave (E)-5-(2-methoxycarbonylethenyl) tubercidin (3) which on treatment with aqueous hydroxide was hydrolyzed to (E)-5-(2-carboxyethenyl) tubercidin (8). Nucleoside 8 was converted to (E)-5-(2-bromoethenyl)tubercidin 9 by N-bromosuccinimide in N.N-dimethylformamide. 3-Chloro-l-butene reacted with 2 and Li2PdCl4 to give a mixture of E and Z 5-(2-buten-l-yl) tubercidin (13,14). Styrene coupled with 2 to give 5-styryltubercidin 12. Finally the mercury could be replaced directly by iodine in DMF to give 5-iodotubercidin (15). Characterization of the C-5 substituted tubercidin derivatives by 13C NMR is discussed.
Document Details
- Document Type
- Technical Report
- Publication Date
- Jan 01, 1980
- Accession Number
- ADA126663
Entities
People
- Donald E. Bergstrom
Organizations
- University of California