摘要
Chiral aryl cyclohex-3-en ether scaffold is widely present in bioactive natural products and drugs.The exploitation of efficient and enantioselective methods for the construction of aryl cyclohex-3-en ether scaffold is significant.Herein we disclose a chiral N,N’-dioxide/Lewis acid complex-catalyzed asymmetric inverse-electron-demand Diels-Alder(IEDDA)reaction using electron-deficient 3-carboalkoxyl-2-pyrones and less electron-enriched aryl enol ethers as reactants.A wide range of non-and 1,2-disubstituted acyclic aryl enol ethers are applicable to deliver diverse chiral bridged bicyclic lactones in high yields and stereoselectivities(up to 96%yield,>20:1 dr,97:3 er).The bridged bicyclic lactone core can be easily converted into chiral aryl cyclohex-3-en ether scaffold.Notably,DFT calculations revealed a stepwise and endo mechanism to explain the high enantioselectivity controlled by the cooperative effect of the steric factors and the dispersion interactions between ligands and enol ethers.
基金
National Natural Science Foundation of China(Nos.22001177,22203023)
Guangdong Pearl River Talent Program(no.2021QN020268)
the Natural Science Foundation of Guangdong Province(Nos.2024A1515012381,2022A1515011859)
Shenzhen Bay Laboratory Startup Fund(No.S201100003)
Major Program of Shenzhen Bay Laboratory(No.S211101001-4)
Shenzhen Bay Qihang Fellow Program(No.QH23001)for generous financial support.
