SYNTHESIS OF HOLOMYCIN AND DERIVATIVES
SYNTHESIS OF HOLOMYCIN AND DERIVATIVES
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DOI：
10.1021/jo00437a023
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发表时间：
1977-01-01
影响因子：
3.6
通讯作者：
ROSS, CH
中科院分区：
文献类型：
--
作者：
ELLIS, JE;FRIED, JH;ROSS, CH
围绕两个关键反应进行了10步合成，得到了霍诺霉素、6-acetamido-5-oxo-4，5-dihydro-1，2-dithiolo[4，3-b]pyrrole(1a)和3-羧基衍生物(1b)。碱对5-methoxalylamino-4-methoxycarbonyl-2-p-methoxyphenyl-2-methyl-1，3-dithiin进行环化，得到含有所需吡咯烷酮环的7-hydroxy-4-methoxycarbonyl-2-p-methoxyphenyl-2-methyl-6-oxo-5，6-dihydro-1，3-dithiino[5，4-b]pyrrole。二硫代缩酮7-p-methoxybenzylamino-4-methoxycarbonyl-2-p-methoxyphenyl-2-methyl-6-oxo-5，6-dihydro-1，3-dithiino[5，4-b]pyrrole的缩合生成环烯醇二硫键6-p-methoxybenzylamino-3-methoxycarbonyl-5-oxo-4，5-dihydro-1，2-dithiolo[4，3-b]pyrrole.进一步的精制得到了全息霉素(1a)和羧基衍生物1b。
Holomycin, 6-acetamido-5-oxo-4,5-dihydro-1,2-dithiolo[4,3-b]pyrrole (1a), and the 3-carboxylated derivative (1b) were prepared by a 10-stage synthesis designed around 2 key reactions. Cyclization of 5-methoxalylamino-4-methoxycarbonyl-2-p-methoxyphenyl-2-methyl-1,3-dithiin by base gave 7-hydroxy-4-methoxycarbonyl-2-p-methoxyphenyl-2-methyl-6-oxo-5,6-dihydro-1,3-dithiino[5,4-b]pyrrole containing the required pyrrolinone ring. A contraction of the dithioketal 7-p-methoxybenzylamino-4-methoxycarbonyl-2-p-methoxyphenyl-2-methyl-6-oxo-5,6-dihydro-1,3-dithiino[5,4-b]pyrrole afforded the cyclic enol disulfide 6-p-methoxybenzylamino-3-methoxycarbonyl-5-oxo-4,5-dihydro-1,2-dithiolo[4,3-b]pyrrole. Further elaboration led to holomycin (1a) and the carboxy derivative 1b.