【摘要】：環(huán)加成構(gòu)筑新的碳碳鍵已成為現(xiàn)代合成化學中重要的手段之一。以苯炔中間體為代表的環(huán)加成反應(yīng)在構(gòu)筑復雜稠環(huán)化合物和天然產(chǎn)物有著獨特的優(yōu)勢,逐漸成為化學家們研究的熱點。本論文系統(tǒng)地探討了在無催化劑、無氧化劑、無保護條件下四炔底物和二苯基二硒醚參與的HDDA反應(yīng)研究,反應(yīng)中避免了中間產(chǎn)物分離過程中帶來資源的浪費,屬于綠色化學。我們將在無水無氧鈀催化條件得到的四炔底物和二苯基二硒醚直接進行反應(yīng),得到了稠合苯并硒酚類化合物。該方法簡便高效,擁有較好的產(chǎn)率,不需要加入導向基團卻有著很好的區(qū)域選擇性。在反應(yīng)的過程中經(jīng)歷了一個HDDA歷程、一個自由基歷程和一個C-H鍵的活化。在90℃的條件下,用多種取代基(p-F,p-CH_3,p-CH_2CH_3,o-Cl等)的四炔底物與二芳基二硒醚反應(yīng),得到了29個含二苯并硒酚骨架的多環(huán)化合物。對得到的產(chǎn)物進行了核磁、紅外、質(zhì)譜等手段進行了表征,得到了其中五個產(chǎn)物的X-ray單晶衍射結(jié)構(gòu)。這種方法提供了一個直接、高效、經(jīng)濟的方式構(gòu)來建稠合二苯并硒酚化合物。
[Abstract]:Cycloaddition to construct new carbon and carbon bonds has become one of the most important methods in modern synthetic chemistry. The cycloaddition reaction represented by the intermediates of phenylacetylene has unique advantages in the construction of complex dense ring compounds and natural products, and has gradually become a hot topic for chemists. In this paper, the HDDA reaction of tetraacetylene substrate and diphenyl diselenide in the presence of no catalyst, no oxidant and no protection has been studied systematically, which avoids the waste of resources in the separation of intermediate products and belongs to green chemistry. In the presence of anhydrous anoxic palladium as catalyst, tetraacetylene substrates and diphenyl diselenides were directly reacted to obtain dense benzo-selenol compounds. The method is simple and efficient, with good yield and good regioselectivity without adding the guided group. During the reaction a HDDA process, a free radical process and a C-H bond activation were observed. At 90 鈩，

本文編號：2272400