Studies on Nucleosides and Nucleotides. XII. Carbon-Chain Extension at 5′-Position of Ribonucleosides

• Published in: Bulletin of the Chemical Society of Japan Vol. 59; no. 3; pp. 869 - 874
• Main Authors: Kimura, Junji, Kobayashi, Hideyuki, Miyahara, Osamu, Mitsunobu, Oyo
• Format: Journal Article
• Language: English
• Published: Tokyo The Chemical Society of Japan 01.03.1986; Chemical Society of Japan
• Subjects: Carbohydrates. Nucleosides and nucleotides; Chemistry; Exact sciences and technology; Nucleosides, nucleotides and oligonucleotides; Organic chemistry; Preparations and properties; Nitronic acid; Purine nucleoside; Ultraviolet spectrum; Ketonucleoside; Ribonucleoside; NMR spectrum; Pyrimidine nucleoside
• ISSN: 0009-2673; 1348-0634
• DOI: 10.1246/bcsj.59.869

2,6-Di-t-butyl-4-nitrophenol reacted with O2-methyluridine, N3-methyluridine or 4-triazolyl-1-(β-D-ribofuranosyl)-2(1H)-pyrimidinone in the presence of diethyl azodicarboxylate and triphenylphosphine selectively at the 5′-position to give the corresponding 4-(nucleosid-5′-yl-aci-nitro)-2,6-di-t-butylcyclohexa-2,5-dienone (aci-nitro ester of nucleoside) in 39–72% yields along with varied amounts of 5′-deoxy-5′-[N,N′-bis(ethoxycarbonyl)hydrazino]nucleosides. By comparison of the reactions of pyrimidine nucleosides having free 2′- and 3′-hydroxyl groups with those of their 2′,3′-O-isopropylidene derivatives, the ratio of aci-nitxo ester to 5′-deoxy-5′-hydrazinonucleoside was affected by the protecting groups as well as the time required for the addition of diethyl azodicarboxylate to a solution of other reactants. Similarly, N1,N6,2′3′-O-tetrabenzoyladenosine afforded the expected aci-nitro ester in 83% yield. The aci-nitro esters prepared were successfully reacted with stabilized phosphoranes such as (ethoxycarbonylmethylene)triphenylphosphorane or (acetylmethylene)triphenylphosphorane giving 1-[(E)-β-D-ribo-hept-5-enofuranosyl]- or 1-[(E)-β-D-ribo-oct-5-enofuranosyl]-pyrimidines and -purines. When the two stage reactions were carried out by one-pot procedure without isolation of aci-nitro esters, overall yields of alkenofuranosylpyrimidines were markedly improved.