Synthesis of vinca alkaloids and related compounds.: 90.: New results in the synthesis of alkaloids with the aspidospermane skeleton.: First total synthesis of (±)-3-oxominovincine
Synthesis of vinca alkaloids and related compounds.: 90.: New results in the synthesis of alkaloids with the aspidospermane skeleton.: First total synthesis of (±)-3-oxominovincine
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DOI：
10.1021/jo9713464
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发表时间：
1997-12-26
影响因子：
3.6
通讯作者：
Szántay, C
中科院分区：
文献类型：
--
作者：
Kalaus, G;Juhász, I;Szántay, C
色胺衍生物1易于与由2，4-戊二酮生成的4-乙酰基-5-溴代-4-烯酸甲酯（9）反应。在分子内脱水和随后的[4 + 2]环加成反应中，反应产物10得到具有D-开环蜘蛛精烷骨架的差向异构体12和13。化合物12直接和13在差向异构化后产生（+/-）-3-氧代氨基长春新碱（14）。14的区域选择性还原提供（+）-米诺新碱（17）。
The tryptamine derivative 1 readily reacted with methyl 4-acetyl-5-bromopent-4-enoate (9) that had been built up from 2,4-pentanedione. On intramolecular dehydration and subsequent [4 + 2] cycloaddition, the reaction product 10 gave the epimers 12 and 13 having the D-secoaspidospermane skeleton. Compound 12 directly and 13 after epimerization yielded (+/-)-3-oxominovincine (14). Regioselective reduction of 14 furnished (+)-minovincine (17).