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Adefovir dipivoxil, GS-840, Bis(pom)PMEA, Piv2PMEA, Hepsera, Preveon(former TM)

阿德福韦酯Chemical Name: 9-[2-[Bis(pivaloyloxymethoxy)phosphorylmethoxy]ethyl]adenine
CAS No. 142340-99-6
项目整合开发状态: Launched-2002
项目研究机构: Inst. Organic Chemistry Biochemistry (Originator), Rega Institute for Medical Research (Originator), Gilead (Licensee), GlaxoSmithKline (Licensee)
合成路线:Adefovir dipivoxil can be obtained by two similar ways:1) The reaction of adenine (I) with 2-(diisopropoxyphosphorylmethoxy)ethyl methanesulfonate (II) by means of cesium carbonate in DMF gives the expected condensation product (III),which is converted into the phosphonic acid (IV) by treatment with trimethylsilyl bromide in acetonitrile (1).Finally,this compound is condensed with chloromethyl pivalate (V) by means of N,N'-dicyclohexylmorpholine-4-carboxamidine in DMF.2) The final condensation of the phosphonic acid (IV) can also be performed with iodomethyl pivalate (VI) in pyridine.
📌 参考资料/链接:
参考文献标题:Prodrug of phosphonates
文献作者:Starrett,J.E.Jr.; Mansuri,M.M.; Martin,J.C.; Tortolani,D.R.; Bronson,J.J.(Bristol-Myers Squibb Co.)
参考来源:EP 0481214; JP 1992230694

📄 详细内容


合成路线:An optimized process for large-scale production of adefovir dipivoxil has been reported:The reaction of adenine (I) with 1,3-dioxolan-2-one (II) by means of NaOH in hot DMF gives 9-(2-hydroxyethyl)adenine (III),which is condensed with diethyl p-toluenesulfonyloxymethylphosphonate (IV) by means of sodium tert-butoxide,(instead of NaH,originally used) in DMF yielding 9-[2-(diethylphosphonomethoxy)ethyl]adenine (V).The hydrolysis of intermediate (V) by means of TMS-Br in hot acetonitrile affords the phosphonic acid (VI),which is finally condensed with chloromethyl pivalate (VII) by means of triethylamine in hot N-methylpyrrolidine.

参考文献标题:Nucleotide analog compsns.
文献作者:Kelly,D.E.; Lee,T.T.K.; Prisbe,E.J.; Schultze,L.M.; Arimilli,M.N.; Manes,L.V.; Munger,J.D.Jr.(Gilead Sciences Inc.)
参考来源:WO 9904774


合成路线:An optimized process for large-scale production of adefovir dipivoxil has been reported:The reaction of adenine (I) with 1,3-dioxolan-2-one (II) by means of NaOH in hot DMF gives 9-(2-hydroxyethyl)adenine (III),which is condensed with diethyl p-toluenesulfonyloxymethylphosphonate (IV) by means of sodium tert-butoxide,(instead of NaH,originally used) in DMF yielding 9-[2-(diethylphosphonomethoxy)ethyl]adenine (V).The hydrolysis of intermediate (V) by means of TMS-Br in hot acetonitrile affords the phosphonic acid (VI),which is finally condensed with chloromethyl pivalate (VII) by means of triethylamine in hot N-methylpyrrolidine.

参考文献标题:Pharmaceutical formulations
文献作者:Dahl,T.C.; Yuan,L.-C.J.(Gilead Sciences Inc.)
参考来源:WO 0035460


合成路线:Adefovir dipivoxil can be obtained by two similar ways:1) The reaction of adenine (I) with 2-(diisopropoxyphosphorylmethoxy)ethyl methanesulfonate (II) by means of cesium carbonate in DMF gives the expected condensation product (III),which is converted into the phosphonic acid (IV) by treatment with trimethylsilyl bromide in acetonitrile (1).Finally,this compound is condensed with chloromethyl pivalate (V) by means of N,N'-dicyclohexylmorpholine-4-carboxamidine in DMF.2) The final condensation of the phosphonic acid (IV) can also be performed with iodomethyl pivalate (VI) in pyridine.

参考文献标题:Synthesis and in vitro evaluation of a phosphonate prodrug: bis(pivaloyloxymethyl) 9-(2-phosphonylmethoxyethyl)adenine
文献作者:Starrett,J.E.Jr.; et al.
参考来源:Antivir Res 1992,19(3),267-73


合成路线:Adefovir dipivoxil can be obtained by two similar ways:1) The reaction of adenine (I) with 2-(diisopropoxyphosphorylmethoxy)ethyl methanesulfonate (II) by means of cesium carbonate in DMF gives the expected condensation product (III),which is converted into the phosphonic acid (IV) by treatment with trimethylsilyl bromide in acetonitrile (1).Finally,this compound is condensed with chloromethyl pivalate (V) by means of N,N'-dicyclohexylmorpholine-4-carboxamidine in DMF.2) The final condensation of the phosphonic acid (IV) can also be performed with iodomethyl pivalate (VI) in pyridine.

参考文献标题:Synthesis,oral bioavailability determination,and in vitro evaluation of prodrugs of the antiviral agent 9-[2-(phosphonomethoxy)ethyl]adenine (PMEA)
文献作者:Starrett,J.E.Jr.; Tortolani,D.R.; Russell,J.; Hitchcock,M.J.M.; Whiterock,V.; Martin,J.C.; Mansuri,M.M.
参考来源:J Med Chem 1994,37(12),1857-64


合成路线:Adefovir dipivoxil can be obtained by two similar ways:1) The reaction of adenine (I) with 2-(diisopropoxyphosphorylmethoxy)ethyl methanesulfonate (II) by means of cesium carbonate in DMF gives the expected condensation product (III),which is converted into the phosphonic acid (IV) by treatment with trimethylsilyl bromide in acetonitrile (1).Finally,this compound is condensed with chloromethyl pivalate (V) by means of N,N'-dicyclohexylmorpholine-4-carboxamidine in DMF.2) The final condensation of the phosphonic acid (IV) can also be performed with iodomethyl pivalate (VI) in pyridine.

参考文献标题:Adefovir Dipivoxil
文献作者:Prous,J.; Graul,A.; Castar,J.
参考来源:Drugs Fut 1997,22(8),825


合成路线:Adefovir dipivoxil can be obtained by two similar ways:1) The reaction of adenine (I) with 2-(diisopropoxyphosphorylmethoxy)ethyl methanesulfonate (II) by means of cesium carbonate in DMF gives the expected condensation product (III),which is converted into the phosphonic acid (IV) by treatment with trimethylsilyl bromide in acetonitrile (1).Finally,this compound is condensed with chloromethyl pivalate (V) by means of N,N'-dicyclohexylmorpholine-4-carboxamidine in DMF.2) The final condensation of the phosphonic acid (IV) can also be performed with iodomethyl pivalate (VI) in pyridine.

参考文献标题:Synthesis,in vitro antiviral evaluation,and stability studies of bis(S-acyl-2-thioethyl) ester derivatives of 9-[2-(phosphonomethoxy)ethyl]adenine (PMEA) as potential PMEA prodrugs with improved oral bioavailability
文献作者:Benzaria,S.; Picano,H.; Johnson,R.; Maury,G.; Imbach,J.-L.; Aubertin,A.-M.; Obert,G.; Gosselin,G.
参考来源:J Med Chem 1996,39(25),4958-65


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