基于分子內(nèi)芳香C-H插入反應(yīng)合成硫雜和磷雜吲哚啉
發(fā)布時(shí)間:2018-08-18 09:36
【摘要】:吲哚和吲哚啉衍生物是一類(lèi)具有生物活性的重要有機(jī)物,同時(shí)在大量的天然產(chǎn)物中具有吲哚或吲哚啉的結(jié)構(gòu)單元。目前,對(duì)于吲哚和吲哚啉衍生物的合成方法有很多種,但是對(duì)于硫雜或磷雜吲哚啉的合成方法卻很有限。吲哚酮是吲哚啉的衍生物之一,其合成方法同樣有很多種,其中通過(guò)分子內(nèi)的芳香C-H插入反應(yīng)是構(gòu)建吲哚酮的一種非常有效且簡(jiǎn)便的方法。由于磺酰基和膦;;粯佣际俏娮踊鶊F(tuán),因此α-吸電子基取代的磺酰胺和膦酰胺中的亞甲基比較活潑,在堿和重氮轉(zhuǎn)移試劑同時(shí)存在的條件下,可以轉(zhuǎn)化為重氮化合物。重氮化合物是良好的卡賓前體,在金屬催化劑、光照或高溫等條件下可以發(fā)生插入反應(yīng)。本文主要以α-吸電子基取代的磺酰胺和膦酰胺為原料,開(kāi)發(fā)了一種基于分子內(nèi)芳香C-H插入反應(yīng)來(lái)合成硫雜和磷吲哚啉的方法。首先,通過(guò)設(shè)計(jì)控制α-吸電子取代基的種類(lèi),選擇性地合成了氮原子上含有芳基或烷基的硫雜吲哚啉。在銅(Ⅱ)催化劑的存在下,重氮磺酰胺作為卡賓前體發(fā)生分子內(nèi)芳香C-H插入反應(yīng)生成硫雜吲哚啉——2,2-二氧代-1,3-二氫苯并[c]異噻唑。α-吸電子取代基為乙氧羰基時(shí),僅可以得到N原子上含有芳基的硫雜吲哚啉。氮原子上含有烷基的硫雜吲哚啉則可以通過(guò)改變?chǔ)?吸電子取代基為苯甲酰基或乙;鶃(lái)實(shí)現(xiàn)。當(dāng)改變?chǔ)?吸電子取代基為N-苯基酰胺基,則可以化學(xué)選擇性地得到α-磺酰胺基的吲哚酮衍生物。其次,用廉價(jià)的CuSO4·5H2O作為催化劑,以重氮苯甲酰基甲基膦酰胺為原料合成磷雜吲哚啉——2-氧代-2-乙氧基-1,3-二氫苯并[d][1,2]磷雜唑。本文主要論述的是,以α-吸電子取代基的磺酰胺和膦酰胺為原料,在堿和重氮轉(zhuǎn)移試劑同時(shí)存在下,得到了良好的卡賓前體重氮化合物中間體,開(kāi)發(fā)出了合成硫雜和磷雜吲哚啉的方法。該法同時(shí)兼有高效簡(jiǎn)便、便于操作、廉價(jià)經(jīng)濟(jì)等優(yōu)點(diǎn)。
[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 偽 -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 偽 -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 偽 -electron-absorbing substituents. In the presence of copper (鈪,
本文編號(hào):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 偽 -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 偽 -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 偽 -electron-absorbing substituents. In the presence of copper (鈪,
本文編號(hào):2189073
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