Synthesis of 4'-substituted cordycepins via benzenesulfenylation at the 4'-position as a key step.
With an aim to synthesize 4'-substituted cordycepins, the 4'-phenylthio precursor 4 was prepared from adenosine through an electrophilic addition to the 3',4'-unsaturated derivative 2 by using NIS/PhSH system. Nucleophilic substitution of 4 with a series of alcohols in the presence of NBS gave the respective 4'-alpha-alkoxy cordycepins 6 as the major stereoisomer. Use of DAST, in stead of alcohol in this reaction, gave the 4'-fluoro analogue 7. The 4'-sulfone derivative 8 obtained by m-CPBA oxidation of 4 was employed for the reaction with organoaluminum reagents. These reactions furnished various types of the 4'-carbon-substituted cordycepins 9.
Kubota
Yutaka
Y
School of Pharmaceutical Sciences, Showa University, Tokyo 142-8555, Japan. y-kubota@pharm.showa-u.ac.jp
Ehara
Mariko
M
Kumamoto
Hiroki
H
Shimada
Hisashi
H
Haraguchi
Kazuhiro
K
Tanaka
Hiromichi
H
D001554:Benzene / Q000737:chemistry*; D003839:Deoxyadenosines / Q000138:chemical synthesis* / Q000737:chemistry; D013416:Sulfamerazine / Q000737:chemistry
D003839:Deoxyadenosines; C012049:sulfaperine; C058120:cordycepin; D001554:Benzene; D013416:Sulfamerazine