氧化重排构建环戊烯二酮(CPD)结构及其在含CPD骨架天然产物仿生全合成中的应用

环戊烯二酮(CPDs)作为具有重要生物活性的基团，存在于如asterredione、madindolines A和B等多种具有显著生物活性的天然产物中。尽管它们的结构和显著的活性使其成为有机化学家理想的合成靶标，迄今为止环戊烯二酮类天然产物仍然缺乏具有普适性的合成策略。受该家属天然产物asterredione生源途径启发，本项目设计新颖的仿生氧化重排缩环反应，模拟自然界中生命体内的有机转化，从苯醌类化合物出发，绿色快捷地构建I（不含季碳中心）、II（含季碳中心）两类环戊烯二酮骨架，并利用手性高价碘等手性氧化剂实现不对称氧化重排合成具有手性季碳中心的II类型环戊烯二酮结构。同时应用该仿生重排反应，建立一条可靠的合成途径，高效地实现天然产物asterredione、madindolines A和B等天然产物的全合成以及它们衍生物、类似物的合成，为新药开发提供物质基础和技术支持。

Cyclopentenediones(CPDs), as important biological activities, exist in an array of remarkably bioactive natural products such as asterredione, madindolines A and B,etc. The combination of their intriguing structures as well as remarkable bioactivities renders CPDs as ideal synthetic targets. Nevertheless, the major issue clouding further study towards this structure motif lies in that strategies accessing to CPDs are not universal. The promising biogenetic pathway of asterredione provides us valuable blueprints for the rapid assembly of natural products bearing CPD skeleton. This project aims to design an innovative biomimetic oxidative rearrangement ring contraction from quinone, which mirrors natural organic transformation in vivo, to efficiently construct the cyclopentenedione skeletons of both type I (without quaternary carbon center) and type II (with quaternary carbon center ). Synthesis of type II CPDs with chiral quaternary carbon center will be pursued through a choreographed asymmetric oxidative rearrangement enabled by chiral oxidants such as hypervalent iodine reagent. Furthermore, efforts will be made to develop a universal synthetic strategy to access the corresponding natural products as well as their analogues and derivatives, aiming to provide enlightenment for new drug development in terms of material and technology.