Total Synthesis of Laurane and Guaiane Sesquiterpenoids via Oxidative Nazarov Reaction  

作　　者：Yuye Chen Wenqing Chen Zhiting Zhang Jing Xu 

机构地区：[1]Shenzhen Grubbs Institute and Department of Chemistry and Guangming Advanced Research Institute and Guangdong Provincial Key Laboratory of Catalysis and Shenzhen Key Laboratory of Small Molecule Drug Discovery and Synthesis,Southern University of Science and Technology,Shenzhen,Guangdong,518055 China

出　　处：《Chinese Journal of Chemistry》2024年第11期1267-1274,共8页中国化学（英文版）

基　　金：support from the National Natural Science Foundation of China(Nos.21971104,22001114 and 22271136);Shenzhen Science,Technology and Innovation Commission(JCYJ20220814203252001);Shenzhen Key Laboratory of Small Molecule Drug Discovery and Synthesis(ZDSYS20190902093215877);Guangdong Provincial Key Laboratory of Catalysis(No.2020B121201002);Guangdong Innovative Program(No.2019BT02Y335);Education Department of Guangdong Province,Key Research Projects in Colleges and Universities in Guangdong Province(2021ZDZX2035);Shenzhen Nobel Prize Scientists Laboratory Project(C17783101),Innovative Team of Universities in Guangdong Province(2020KCXTD016);Guangdong Natural Science Foundation(2022A1515010456)is greatly appreciated.

摘　　要：As one of the most common structural motifs in natural products,cyclopentenones usually can be fabricated by Nazarov cyclization using divinyl ketones or functionalized tertiary divinyl carbinols(TDCs)as substrates.However,straightforward method for transforming unfunctionalized TDCs to their corresponding cyclopentenones is currently lacking.Herein,we wish to report the total syntheses of four structurally distinct terpenoids,namely laurane-type marine sesquiterpenoids isolaurene,debromoaplysin and aplysin,and guaiane sesquiterpenoid guaiadienone A,all using a novel synthetic method,named oxidative Nazarov cyclization,as the key step.This work demonstrated our robust method is suitable for synthesizing various highly substituted cyclopentenones.

关 键 词：Total synthesis Synthetic methods SESQUITERPENOIDS Oxidative Nazarov reaction ELECTROCYCLIZATION Oxoammonium salt Pericyclic reaction ANNULATION 

分 类 号：O62[理学—有机化学]