Nucleophilic addition of benzenethiol to 1',2'-unsaturated nucleosides: 1'-C-phenylthio-2'-deoxynucleosides as anomeric radical precursors.
The addition reaction of benzenethiol to the glycal portion of 1',2'-unsaturated uridine proceeds efficiently in the presence of Et(3)N. The mechanism involves nucleophilic attack of thiolate at the anomeric position in the rate-determining step, wherein conjugation between the nucleobase and the glycal portion is crucial. The derivative having a methyl group either at the 2'- or 6-position did not undergo this addition reaction, due to their sterically prohibited coplanarity. The 1',2'-unsaturated derivatives of thymine and adenine can also be used as substrates for this addition reaction. It was also shown that the resulting 1'-C-phenylthio-2'-deoxynucleosides serve as precursors for radical-mediated C-C bond formation at the anomeric position.
School of Pharmaceutical Sciences, Showa University, 1-5-8 Hatanodai, Shinagawa-ku, Tokyo 142-8555, Japan. hirotnk@pharm.showa-u.ac.jp
Hiroki
H
Kumamoto
Miki
M
Murasaki
Kazuhiro
K
Haraguchi
Aki
A
Anamura
Hiromichi
H
Tanaka
D002384:Catalysis; D002851:Chromatography, High Pressure Liquid; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D009705:Nucleosides / Q000737:chemistry*; D013237:Stereoisomerism; D013872:Thionucleosides / Q000737:chemistry*; D014529:Uridine / Q000737:chemistry*
D009705:Nucleosides; D013872:Thionucleosides; D014529:Uridine