TMA-230

Chemical Name: (+)-(5R,6S)-6-[1(R)-Hydroxyethyl]-2-(3-pyridyl)-2-penem-3-carboxylic acid acetoxymethyl ester
CAS No. 113141-80-3
项目整合开发状态: Phase II
项目研究机构: Novartis (Originator), Takeda (Licensee)
合成路线:2) The reaction of 3-pyridylcarbonyl chloride (I) with (3S,4R)-2-[3-[1(R)-(allyloxycarbonyloxy)ethyl]-2-oxo-4-sulfanylazetidin-1-yl]-2-(triphenylphosphoranylidene)acetic acid allyl ester silver salt (VII) in dichloromethane containing pyridine gives the substituted phosphorane (VIII),which is cyclized in refluxing toluene to afford (5R,6S)-6-[1(R)-(allyloxycarbonyloxy)ethyl]-2-(3-pyridyl)-2-penem-3-carboxylic acid allyl ester (IX).The deprotection of (IX) with tetrakis(triphenylphosphine)palladium,tributyltin hydride and NaHCO3 in THF gives the free acid (X) as the sodium salt,which is finally esterified with bromomethyl acetate.
📌 参考资料/链接:
参考文献标题:2-Pyridyl-penem cpds
文献作者:Lang,M.(Novartis AG)
参考来源:EP 0246187; JP 1987263183; US 4826832

📄 详细内容


合成路线:1) The reaction of 3-pyridylcarbonyl chloride (I) with (3S,4R)-2-[3-[1(R)-hyroxyethyl]-2-oxo-4-sulfanylazetidin-1-yl]-2-(triphenylphosphoranylidene)acetic acid allyl ester silver salt (II) in dichloromethane containing pyridine gives the substituted phosphorane (III),which is cyclized in refluxing benzene to afford (5R,6S)-6-[1(R)-hydroxyethyl]-2-(3-pyridyl)-2-penem-3-carboxylic acid allyl ester (IV).The deprotection of (IV) by means of triphenylphosphine,tetrakis(triphenylphosphine)palladium and acetic acid yields the free acid (V),which is finally esterified with bromomethyl acetate (VI) in DMF.

合成路线:2) The reaction of 3-pyridylcarbonyl chloride (I) with (3S,4R)-2-[3-[1(R)-(allyloxycarbonyloxy)ethyl]-2-oxo-4-sulfanylazetidin-1-yl]-2-(triphenylphosphoranylidene)acetic acid allyl ester silver salt (VII) in dichloromethane containing pyridine gives the substituted phosphorane (VIII),which is cyclized in refluxing toluene to afford (5R,6S)-6-[1(R)-(allyloxycarbonyloxy)ethyl]-2-(3-pyridyl)-2-penem-3-carboxylic acid allyl ester (IX).The deprotection of (IX) with tetrakis(triphenylphosphine)palladium,tributyltin hydride and NaHCO3 in THF gives the free acid (X) as the sodium salt,which is finally esterified with bromomethyl acetate.

参考文献标题:TMA-230
文献作者:Mealy,M.; Castar,J.
参考来源:Drugs Fut 1996,21(5),493


合成路线:1) The reaction of 3-pyridylcarbonyl chloride (I) with (3S,4R)-2-[3-[1(R)-hyroxyethyl]-2-oxo-4-sulfanylazetidin-1-yl]-2-(triphenylphosphoranylidene)acetic acid allyl ester silver salt (II) in dichloromethane containing pyridine gives the substituted phosphorane (III),which is cyclized in refluxing benzene to afford (5R,6S)-6-[1(R)-hydroxyethyl]-2-(3-pyridyl)-2-penem-3-carboxylic acid allyl ester (IV).The deprotection of (IV) by means of triphenylphosphine,tetrakis(triphenylphosphine)palladium and acetic acid yields the free acid (V),which is finally esterified with bromomethyl acetate (VI) in DMF.
参考文献标题:Synthesis and structure-activity relations in the class 2-(pyridyl)penems
文献作者:Bedeschi,A.; Visentin,G.; Perrone,E.; Giudici,F.; Zarini,F.; Franceschi,G.; Meinardi,G.; Castellani,P.; Jabes,D.; Rossi,R.; et al.
参考来源:J Antibiot 1990,43(3),306-13