基于分子内芳香C-H插入反应合成硫杂和磷杂吲哚啉
发布时间：2018-08-18 09:36
【摘要】：吲哚和吲哚啉衍生物是一类具有生物活性的重要有机物,同时在大量的天然产物中具有吲哚或吲哚啉的结构单元。目前,对于吲哚和吲哚啉衍生物的合成方法有很多种,但是对于硫杂或磷杂吲哚啉的合成方法却很有限。吲哚酮是吲哚啉的衍生物之一,其合成方法同样有很多种,其中通过分子内的芳香C-H插入反应是构建吲哚酮的一种非常有效且简便的方法。由于磺酰基和膦酰基同酰基一样都是吸电子基团,因此α-吸电子基取代的磺酰胺和膦酰胺中的亚甲基比较活泼,在碱和重氮转移试剂同时存在的条件下,可以转化为重氮化合物。重氮化合物是良好的卡宾前体,在金属催化剂、光照或高温等条件下可以发生插入反应。本文主要以α-吸电子基取代的磺酰胺和膦酰胺为原料,开发了一种基于分子内芳香C-H插入反应来合成硫杂和磷吲哚啉的方法。首先,通过设计控制α-吸电子取代基的种类,选择性地合成了氮原子上含有芳基或烷基的硫杂吲哚啉。在铜(Ⅱ)催化剂的存在下,重氮磺酰胺作为卡宾前体发生分子内芳香C-H插入反应生成硫杂吲哚啉——2,2-二氧代-1,3-二氢苯并[c]异噻唑。α-吸电子取代基为乙氧羰基时,仅可以得到N原子上含有芳基的硫杂吲哚啉。氮原子上含有烷基的硫杂吲哚啉则可以通过改变α-吸电子取代基为苯甲酰基或乙酰基来实现。当改变α-吸电子取代基为N-苯基酰胺基,则可以化学选择性地得到α-磺酰胺基的吲哚酮衍生物。其次,用廉价的CuSO4·5H2O作为催化剂,以重氮苯甲酰基甲基膦酰胺为原料合成磷杂吲哚啉——2-氧代-2-乙氧基-1,3-二氢苯并[d][1,2]磷杂唑。本文主要论述的是,以α-吸电子取代基的磺酰胺和膦酰胺为原料,在碱和重氮转移试剂同时存在下,得到了良好的卡宾前体重氮化合物中间体,开发出了合成硫杂和磷杂吲哚啉的方法。该法同时兼有高效简便、便于操作、廉价经济等优点。
[Abstract]:Indole and indoline derivatives are a kind of important organic compounds with biological activity, and also have the structural units of indole or indole in a large number of natural products. At present, there are many methods for the synthesis of indoline and indoline derivatives, but the synthesis methods of indoline and indoline derivatives are very limited. Indole ketone is one of the derivatives of indole, and there are many methods for its synthesis, among which the intramolecular aromatic C-H insertion reaction is a very effective and simple method for the construction of indole ketone. Since sulfonyl and phosphonyl groups are electron-absorbing groups like acyl groups, methylene in sulfamides and phosphonamide substituted by 伪 -electron-absorbing groups is more active, under the condition of the presence of both alkali and diazo transfer reagents. It can be converted into diazo compounds. Diazo compounds are good carbene precursors and can be inserted under metal catalyst, illumination or high temperature. In this paper, a new method for the synthesis of thiaza- and indoline based on the intramolecular aromatic C-H insertion reaction was developed from 伪 -electron-absorbing sulfonamide and phosphonamide. Firstly, the thiazindolines containing aryl or alkyl on the nitrogen atom were selectively synthesized by designing and controlling the kinds of 伪 -electron-absorbing substituents. In the presence of copper (鈪，
本文编号：2189073
[Abstract]:Indole and indoline derivatives are a kind of important organic compounds with biological activity, and also have the structural units of indole or indole in a large number of natural products. At present, there are many methods for the synthesis of indoline and indoline derivatives, but the synthesis methods of indoline and indoline derivatives are very limited. Indole ketone is one of the derivatives of indole, and there are many methods for its synthesis, among which the intramolecular aromatic C-H insertion reaction is a very effective and simple method for the construction of indole ketone. Since sulfonyl and phosphonyl groups are electron-absorbing groups like acyl groups, methylene in sulfamides and phosphonamide substituted by 伪 -electron-absorbing groups is more active, under the condition of the presence of both alkali and diazo transfer reagents. It can be converted into diazo compounds. Diazo compounds are good carbene precursors and can be inserted under metal catalyst, illumination or high temperature. In this paper, a new method for the synthesis of thiaza- and indoline based on the intramolecular aromatic C-H insertion reaction was developed from 伪 -electron-absorbing sulfonamide and phosphonamide. Firstly, the thiazindolines containing aryl or alkyl on the nitrogen atom were selectively synthesized by designing and controlling the kinds of 伪 -electron-absorbing substituents. In the presence of copper (鈪，
本文编号：2189073
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