TOTAL SYNTHESIS OF INDOLE AND DIHYDROINDOLE ALKALOIDS .1. INTRODUCTION AND TRANSANNULAR CYCLIZATION APPROACH
TOTAL SYNTHESIS OF INDOLE AND DIHYDROINDOLE ALKALOIDS .1. INTRODUCTION AND TRANSANNULAR CYCLIZATION APPROACH
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DOI：
10.1021/ja00709a048
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发表时间：
1970-01-01
影响因子：
15
通讯作者：
BROWN, RT
中科院分区：
文献类型：
--
作者：
KUTNEY, JP;PIERS, E;BROWN, RT
介绍了跨环环化反应及其在吲哚和二氢吲哚生物碱合成中的应用。通过将4/3-dihydrocleavamine（I）转化为7/3-ethyl-5-desethyiaspidospermidine（V），首次在实验室成功实现了该方法。从（-）-白坚木胺（IX）部分合成（+）-Aspidospermidine（X）说明了该方法对天然Aspido-sperma系列的扩展。通过对Na-乙酰基衍生物VI的Nb-甲基碘的X-射线分析确定了该反应的立体化学。这项研究提供了第一个具有Aspidosperma骨架的化合物，其绝对构型是可用的。它的重要性，在天然Aspidosperma系列的绝对配置的确定。
An introduction to the transannular cyclization reaction and its application to indole and dihydroindole alkaloid syntheses is presented. The first successful laboratory realization of this process has been accomplished by converting 4/3-dihydrocleavamine (I) into 7/3-ethyl-5-desethyiaspidospermidine (V). The partial synthesis of (+)-aspidospermidine (X) from (—)-quebrachamine (IX) illustrates an extension of this approach to the natural Aspido-sperma series. The stereochemistry of this reaction has been established by X-ray analysis on the Nb-methiodide of the Na-acetyl derivative VI. This study made available the first compound bearing the Aspidosperma skeleton for which an absolute configuration was available. Its importance in connection with the determination of absolute configuration in the natural Aspidosperma series is noted.