Synthesis of 1-(5'-O-benzoyl-3'-deoxy-beta-D-glycero-pentofuran-2'-ulosyl)uracil and its alpha-anomer by [1,2]-hydride shift.
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.
Minamoto
K
K
Institute of Applied Organic Chemistry, Faculty of Engineering, Nagoya University, Japan.
Fujiwara
N
N
Hamano
Y
Y
Eguchi
S
S
D013237:Stereoisomerism; D014529:Uridine / Q000031:analogs & derivatives* / Q000138:chemical synthesis
C062352:1-(5'-O-benzoyl-3'-deoxypentofuran-2'-ulosyl)uracil; D014529:Uridine