Highly stereoselective synthesis of aristeromycin through dihydroxylation of 4-aryl-1-azido-2-cyclopentenes.
Dihydroxylation of 4-aryl-1-azido-2-cyclopentenes 6, in which an aryl group is used as a synthetic equivalent of CH(2)OH, was studied to improve the low to moderate stereoselectivity previously reported for cyclopentenes 3 possessing CH(2)X and nitrogen atom-containing groups. 2-Furyl, Ph, and p-MeOC(6)H(4) groups were chosen as the aryl groups. Compounds 6a-c possessing such aryl groups were prepared by CuCN-catalyzed reaction between 2-cyclopentene-1,4-diol monoacetate 9 and the corresponding Grignard reagents followed by substitution of the hydroxyl group with (PhO)(2)P(=O)N(3). The desired diols 7a-c were obtained with higher selectivities of >7:1 when dihydroxylation of 6a-c was carried out at 0 degrees C with OsO(4) (catalyst) and NMO in a mixed solvent of MeCN, THF, t-BuOH, and H(2)O. Among them, the furyl compound recorded the highest selectivity of 14:1. The furyl and azido groups on diol 7a were converted into hydroymethyl and adeninyl groups, respectively, to produce acetonide 2, which upon hydrolysis affords aristeromycin 1.
Ainai
Takauki
T
Department of Biomolecular Engineering, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama 226-8501, Japan.
Wang
Yong-Gang
YG
Tokoro
Yuko
Y
Kobayashi
Yuichi
Y
D000241:Adenosine / Q000031:analogs & derivatives* / Q000138:chemical synthesis* / Q000737:chemistry; D001386:Azides / Q000737:chemistry*; D001555:Benzene Derivatives / Q000737:chemistry*; D003517:Cyclopentanes / Q000737:chemistry*; D006900:Hydroxylation; D008968:Molecular Conformation; D013237:Stereoisomerism
D001386:Azides; D001555:Benzene Derivatives; D003517:Cyclopentanes; C030034:aristeromycin; D000241:Adenosine