Synthesis and Structure Assignments of Novel Azolinone Ribonucleosides

Ribosidation of a series of azolinones was achieved via silylation and SnCl(,4) catalysis. Ribosidation of 4-imidazolin-2-one gave 1-(beta)-D-ribofuranosyl-4-imidazolin-2-one; of 1,2,4-triazolin-3-one gave 1-, 2-, and 4-(beta)-D-ribofuranosyl-1,2,4-triazolin-3-one, and 2,4-bis-(beta)-D-ribofuranosyl-1,2,4-triazolin-3-one; and of 2-tetrazolin-5-one gave 1-(beta)-D-ribofuranosyl-2-tetrazolin-5-one and 1,4-bis-(beta)-D-ribofuranosyl-2-tetrazolin-5-one. Structure assignments were based on microanalyses and ('1)H and ('13)C NMR spectra. The triazolinone mono-riboside isomer structures are differentiated by ('13)C NMR long-range coupling patterns, and two of the assignments were confirmed by X-ray crystallography. Improved syntheses were developed for two of the ribosides by fashioning the azolinone rings onto 2,3,5-tri-O-benzoylribofuranosyl isocyanate. Reaction of 2,3,5-tri-O-benzoylribofuranosyl isocyanate with (alpha)-aminoacetaldehyde diethyl acetal gave N-(2,2-diethoxyethyl)-N'-(beta)-D-(2,3,5-tri-O-benzoylribofuranosyl)-4-imidazolin-2-one in the presence of acid. Addition of formic acid hydrazide to 2,3,5-tri-O-benzoylribofuranosyl isocyanate gave 1-formyl-4-(beta)-D-(2,3,5-tri-O-benzoyl-ribofuranosyl)semicarbazide, which gave 4-(beta)-D-(2,3,5-tri-O-benzoylribofuranosyl)-1,2,4-triazolin-3-one upon dehydrative silylation. Methyl N-carbomethoxyformimidate was synthesized as a possible reagent for the synthesis of the other 1,2,4-triazolin-3-one products.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2014

Author dc:creator

• Haines, David Richard

• Chemistry, Organic

Language dc:language

eng

Identifier

(UMI)AAI8203477

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/67290