钯催化的碳-氢/氮-氢键活化实现的吲哚新合成法

吲哚类生物碱广泛分布于自然界中，具有多样的生理药理活性。早期的吲哚合成是通过酸碱催化下的环合反应来实现；近年来，利用过渡金属催化的偶联反应实现了各种取代吲哚的合成，但是以未活化的苯胺衍生物为底物通过偶联反应实现C3位单取代的吲哚衍生物尚未见报道。本文以乙酰苯胺与丙烯酸丁酯为底物，通过条件筛选获得最优条件：以醋酸钯为催化剂、2-碘酰基苯甲酸为氧化剂、对甲苯磺酸为添加剂、溶剂选用乙酸/甲苯，并在优化条件下顺利获得C3位单取代的吲哚衍生物。接着进行底物的拓展，均以中等偏上的收率获得相应的产物，丰富了吲哚衍生物的合成体系,最后再利用高分辨质谱和核磁共振氢谱对产物进行表征。
关键词：吲哚；偶联；C-H键活化；N-H键活化

Palladium catalyzed carbon - hydrogen/nitrogen - hydrogen bond to new methods of synthesis of indole

Abstract: Indole alkaloids widely distributed in nature, have a great diversity of physiological and pharmacological activities. Early indole synthesis was done by acid and alkali catalytic cyclization reaction. For the past few years, make use of transition metal catalyzed coupling reaction implements variously instead of indole synthesis, but there has not been reported that not activated aniline derivatives by coupling reactions to obtain C3-substrate indole derivatives. In this paper, acetanilide and butyl acrylate as the substrates, by screening to obtain the optimum condition: Palladium acetate as catalyst, IBX as oxidant, p-TsOH as additive, acetic acid/toluene as solvent, obtain the C3 a single instead of indole derivatives. Then use the optimal conditions for the expansion of the substrates, with average yields obtained the corresponding products, enriched the synthesis of indole system. Finally, according the high resolution mass spectrometry and 1H NMR to characterized the products.
Keywords: indole; coupling; C - H activation; N - H activation

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