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.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.
