合成路线:The benzoylation of 2'-deoxy-5-iodouridine (I) with benzoyl chloride by means of pyridine in dichloromethane gives 5'-O-benzoyl-2'-deoxy-5-iodouridine (II),which is treated with benzyl trichloroacetimidate (III) and trifluoromethanesulfonic acid in dichloromethane - THF to afford the 3'-O-benzyl derivative (IV).The hydrolysis of (IV) with sodium ethoxide in ethanol yields 3'-O-benzyl-2'-deoxy-5-iodouridine (V),which is finally trifluoromethylated with bromotrifluoromethane and copper in pyridine-DMF by means of dimethylaminopyridine.The tritylation of 2'-deoxyuridine (IX) with trityl chloride in hot pyridine gives 2'-deoxy-5'-O-trityluridine (X),which is benzylated with benzyl chloride and NaH in THF yielding 3'-O-benzyl-2'-deoxy-5'-O-trityluridine (XI).The photochemical trifluoromethylation of (XI) with N-nitroso-N-(trifluoromethyl)trifluoromethanesulfonamide and biacetyl in acetonitrile irradiated with a high-pressure Hg lamp in a glass tube at room temperature affords 3'-O-benzyl-2'-deoxy-5-(trifluoromethyl-5'-O-trityluridine (XII),which is finally deprotected with HCl in methanol.
参考文献标题:Method for the preparation of 3'-O-benzyl-2'-deoxy-beta-uridines
文献作者:Yasumoto,M.; Matsumoto,H.; Tada,Y.; Kobayashi,K.; Noguchi,K.(Taiho Pharmaceutical Co.,Ltd.)
参考来源:JP 1987187484
合成路线:The benzoylation of 2'-deoxy-5-(trifluoromethyl)uridine (VI) with benzoyl chloride by means of triethylamine in dimethylacetamide gives 3-benzoyl-2'-deoxy-5-(trifluoromethyl)uridine (VII),which is benzylated with benzyl bromide and silver oxide in refluxing 2-butanone to afford 3-benzoyl-3'-O-benzyl-2'-deoxy-5-(trifluoromethyl)uridine (VIII).Finally,this compound is debenzoylated with 30% aqueous ammonia at room temperature.The deprotection of 2'-deoxy-3'-O-(thiobenzoyl)-5-(trifluoromethyl)-5'-O-trityluridine (XIII) with 0.1N HCl gives 2'-deoxy-3'-O-(thiobenzoyl)-5-(trifluoromethyl)uridine (XIV),which is submitted to desulfurization with Raney-Ni in THF.
参考文献标题:Method for the preparation of 5-trifluromethyl-2'-deoxy-beta-uridines
文献作者:Noguchi,K.; Yasumoto,M.; Kobayashi,K.(Taiho Pharmaceutical Co.,Ltd.)
参考来源:JP 1988145296
合成路线:The benzoylation of 2'-deoxy-5-(trifluoromethyl)uridine (VI) with benzoyl chloride by means of triethylamine in dimethylacetamide gives 3-benzoyl-2'-deoxy-5-(trifluoromethyl)uridine (VII),which is benzylated with benzyl bromide and silver oxide in refluxing 2-butanone to afford 3-benzoyl-3'-O-benzyl-2'-deoxy-5-(trifluoromethyl)uridine (VIII).Finally,this compound is debenzoylated with 30% aqueous ammonia at room temperature.The deprotection of 2'-deoxy-3'-O-(thiobenzoyl)-5-(trifluoromethyl)-5'-O-trityluridine (XIII) with 0.1N HCl gives 2'-deoxy-3'-O-(thiobenzoyl)-5-(trifluoromethyl)uridine (XIV),which is submitted to desulfurization with Raney-Ni in THF.
参考文献标题:Studies on antitumor agents.IX.Synthesis of 3'-O-benzyl-2'-deoxy-5-trifluromethyluridine
文献作者:Yamashita,J.-I.; Matsumoto,H.; Kobayashi,K.; Noguchi,K.; Yasumoto,M.; Ueda,T.
参考来源:Chem Pharm Bull 1989,37(9),2287-92
合成路线:The benzoylation of 2'-deoxy-5-iodouridine (I) with benzoyl chloride by means of pyridine in dichloromethane gives 5'-O-benzoyl-2'-deoxy-5-iodouridine (II),which is treated with benzyl trichloroacetimidate (III) and trifluoromethanesulfonic acid in dichloromethane - THF to afford the 3'-O-benzyl derivative (IV).The hydrolysis of (IV) with sodium ethoxide in ethanol yields 3'-O-benzyl-2'-deoxy-5-iodouridine (V),which is finally trifluoromethylated with bromotrifluoromethane and copper in pyridine-DMF by means of dimethylaminopyridine.The tritylation of 2'-deoxyuridine (IX) with trityl chloride in hot pyridine gives 2'-deoxy-5'-O-trityluridine (X),which is benzylated with benzyl chloride and NaH in THF yielding 3'-O-benzyl-2'-deoxy-5'-O-trityluridine (XI).The photochemical trifluoromethylation of (XI) with N-nitroso-N-(trifluoromethyl)trifluoromethanesulfonamide and biacetyl in acetonitrile irradiated with a high-pressure Hg lamp in a glass tube at room temperature affords 3'-O-benzyl-2'-deoxy-5-(trifluoromethyl-5'-O-trityluridine (XII),which is finally deprotected with HCl in methanol.
参考文献标题:Studies on antitumor agents.8.Antitumor activities of O-alkyl derivatives of 2'-deoxy-5-(trifluoromethyl)uridine and 2'-deoxy-5-fluorouridine
文献作者:Yamashita,J.-I.; Takeda,S.; Matsumoto,H.; Unemi,N.; Yasumoto,M.
参考来源:J Med Chem 1989,32(1),136-139
合成路线:The benzoylation of 2'-deoxy-5-iodouridine (I) with benzoyl chloride by means of pyridine in dichloromethane gives 5'-O-benzoyl-2'-deoxy-5-iodouridine (II),which is treated with benzyl trichloroacetimidate (III) and trifluoromethanesulfonic acid in dichloromethane - THF to afford the 3'-O-benzyl derivative (IV).The hydrolysis of (IV) with sodium ethoxide in ethanol yields 3'-O-benzyl-2'-deoxy-5-iodouridine (V),which is finally trifluoromethylated with bromotrifluoromethane and copper in pyridine-DMF by means of dimethylaminopyridine.The tritylation of 2'-deoxyuridine (IX) with trityl chloride in hot pyridine gives 2'-deoxy-5'-O-trityluridine (X),which is benzylated with benzyl chloride and NaH in THF yielding 3'-O-benzyl-2'-deoxy-5'-O-trityluridine (XI).The photochemical trifluoromethylation of (XI) with N-nitroso-N-(trifluoromethyl)trifluoromethanesulfonamide and biacetyl in acetonitrile irradiated with a high-pressure Hg lamp in a glass tube at room temperature affords 3'-O-benzyl-2'-deoxy-5-(trifluoromethyl-5'-O-trityluridine (XII),which is finally deprotected with HCl in methanol.
合成路线:The benzoylation of 2'-deoxy-5-(trifluoromethyl)uridine (VI) with benzoyl chloride by means of triethylamine in dimethylacetamide gives 3-benzoyl-2'-deoxy-5-(trifluoromethyl)uridine (VII),which is benzylated with benzyl bromide and silver oxide in refluxing 2-butanone to afford 3-benzoyl-3'-O-benzyl-2'-deoxy-5-(trifluoromethyl)uridine (VIII).Finally,this compound is debenzoylated with 30% aqueous ammonia at room temperature.The deprotection of 2'-deoxy-3'-O-(thiobenzoyl)-5-(trifluoromethyl)-5'-O-trityluridine (XIII) with 0.1N HCl gives 2'-deoxy-3'-O-(thiobenzoyl)-5-(trifluoromethyl)uridine (XIV),which is submitted to desulfurization with Raney-Ni in THF.
参考文献标题:FTC-092
文献作者:Hoshi,A.; Prous,J.; Castar,J.
参考来源:Drugs Fut 1990,15(8),790
产品链接: CAS No. 96141-37-6››