The diastereoselectivity of conventional polyene cyclization reactions is highly dependent on the configuration of the internal alkenes,where E-poly enes provide trans-decalins,while Z-polyenes offer cis-decalins.Alth...The diastereoselectivity of conventional polyene cyclization reactions is highly dependent on the configuration of the internal alkenes,where E-poly enes provide trans-decalins,while Z-polyenes offer cis-decalins.Although polyene cyclization has evolved into a reliable and widely used strategy for the construction of trans-decalin frameworks of terpene and steroid natural products,its application for cis-decalin framework is extremely challenging.展开更多
A direct strategy toward the synthesis of functionalized abietane-type diterpenes and related polycyclic molecules was developed through an Au-catalyzed 1,3-acyloxy migration/cyclization/electrophilic aromatic substit...A direct strategy toward the synthesis of functionalized abietane-type diterpenes and related polycyclic molecules was developed through an Au-catalyzed 1,3-acyloxy migration/cyclization/electrophilic aromatic substitution cascade.Unlike the known polyene-type cyclization strategies for the construction of abietane-type diterpene skeletons,propargylic ester groups were used for the cyclization process,which can readily lead to the key skeleton with C2 and C3 functionalization.As a demonstration of the potential application of this tandem reaction,a collective total synthesis of(±)-2-ketoferruginol,(±)-fleuryinol B,(±)-salviol,(±)-2β-acetoxyferruginol,and(±)-2β-acetoxysugiyl methyl ether was achieved.Among these molecules,(±)-fleuryinol B and(±)-2β-acetoxyferruginol were synthesized for the first time.展开更多
基金supported by the National Natural Science Foundation of China(nos.21778025,91853114,and 2193303)the Natural Science Foundation of Jiangxi Province(no.20202ACBL203004).
文摘The diastereoselectivity of conventional polyene cyclization reactions is highly dependent on the configuration of the internal alkenes,where E-poly enes provide trans-decalins,while Z-polyenes offer cis-decalins.Although polyene cyclization has evolved into a reliable and widely used strategy for the construction of trans-decalin frameworks of terpene and steroid natural products,its application for cis-decalin framework is extremely challenging.
基金supported by the National Natural Science Foundation of China(nos.21472077 and 21772071)Department of Education of Guangdong Province(nos.2017KTSCX185,2017KSYS010,2016KCXTD005,and 2019KZDXM035).
文摘A direct strategy toward the synthesis of functionalized abietane-type diterpenes and related polycyclic molecules was developed through an Au-catalyzed 1,3-acyloxy migration/cyclization/electrophilic aromatic substitution cascade.Unlike the known polyene-type cyclization strategies for the construction of abietane-type diterpene skeletons,propargylic ester groups were used for the cyclization process,which can readily lead to the key skeleton with C2 and C3 functionalization.As a demonstration of the potential application of this tandem reaction,a collective total synthesis of(±)-2-ketoferruginol,(±)-fleuryinol B,(±)-salviol,(±)-2β-acetoxyferruginol,and(±)-2β-acetoxysugiyl methyl ether was achieved.Among these molecules,(±)-fleuryinol B and(±)-2β-acetoxyferruginol were synthesized for the first time.
