Synthesis of 1- (5'-O-benzoyl-3'-deoxy-beta-D-glycero-pentofuran-2'-ulosyl) uracil and its alpha-anomer by [1,2]-hydride shift
Minamoto, K.; Fujiwara, N.; Hamano, Y.; Eguchi, S.
Nucleic Acids Symposium Series 21: 121-122
1989
ISSN/ISBN: 0261-3166 PMID: 2608457 Document Number: 336270
In contrast with direct tosylation of 5'-O-benzoyl- (1d) or 5'-O-pivaloyl-1-beta-D-lyxofuranosyl-uracil (1e) with TsCl/pyridine, tosylation of the 2', 3'-O-dibutylstannylene derivatives (4d,e) of these compounds proved to give the 3'-O-tosyl derivatives 2d, e selectively. Coversion of 2d as a model to 1-(5'-O-benzoyl-3'-deoxy-beta-D-glycero-pentofuran-2'-ulosyl )uracil (5-beta) by base-induced [1,2]-hydride shift was examined under various reaction conditions, and the alpha/beta ratio of the product mixture (5-alpha, beta) determined by 1H NMR spectroscopy in each case. The BzOLi/DMF combination has proved to be most profitable for obtaining 5-beta.