Total Synthesis of Sculponin U through a Photoinduced Radical Cascade Cyclization
Wei Cao
College of Chemistry, Sichuan University, 29 Wangjiang Rd., Chengdu, Sichuan, 610064 China
Search for more papers by this authorZhen Wang
College of Chemistry, Sichuan University, 29 Wangjiang Rd., Chengdu, Sichuan, 610064 China
Search for more papers by this authorYan Hao
College of Chemistry, Sichuan University, 29 Wangjiang Rd., Chengdu, Sichuan, 610064 China
Search for more papers by this authorProf. Dr. Tianli Wang
College of Chemistry, Sichuan University, 29 Wangjiang Rd., Chengdu, Sichuan, 610064 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Shaomin Fu
College of Chemistry, Sichuan University, 29 Wangjiang Rd., Chengdu, Sichuan, 610064 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Bo Liu
College of Chemistry, Sichuan University, 29 Wangjiang Rd., Chengdu, Sichuan, 610064 China
Search for more papers by this authorWei Cao
College of Chemistry, Sichuan University, 29 Wangjiang Rd., Chengdu, Sichuan, 610064 China
Search for more papers by this authorZhen Wang
College of Chemistry, Sichuan University, 29 Wangjiang Rd., Chengdu, Sichuan, 610064 China
Search for more papers by this authorYan Hao
College of Chemistry, Sichuan University, 29 Wangjiang Rd., Chengdu, Sichuan, 610064 China
Search for more papers by this authorProf. Dr. Tianli Wang
College of Chemistry, Sichuan University, 29 Wangjiang Rd., Chengdu, Sichuan, 610064 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Shaomin Fu
College of Chemistry, Sichuan University, 29 Wangjiang Rd., Chengdu, Sichuan, 610064 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Bo Liu
College of Chemistry, Sichuan University, 29 Wangjiang Rd., Chengdu, Sichuan, 610064 China
Search for more papers by this authorGraphical Abstract
The total synthesis of sculponin U, a C20-oxygenated kaurane diterpenoid, was completed. The hexanone-fused bicyclo[3.2.1]octane skeleton was strategically established by a photoinduced electron transfer, generating a cationic radical intermediate from a silyl enolate.
Abstract
We have accomplished the total synthesis of sculponin U, a polycyclic C-20-oxygenated kaurane diterpenoid featuring a 7,20-lactone-hemiketal bridge, through a radical cascade cyclization triggered by photoinduced electron transfer (PET) of a silyl enolate to form the cyclohexanone-fused bicyclo[3.2.1]octane skeleton. Other key points in our synthetic strategy encompass a Diels–Alder reaction to construct the middle six-membered ring of sculponin U, and an intramolecular radical cyclization induced by iron-catalyzed hydrogen atom transfer to close the western cyclohexane ring. Successful preparation of the enantiopure silyl enolate as the PET precursor enables the asymmetric total synthesis of sculponin U, opening a new avenue for divergent syntheses of structurally related C-20-oxygenated kaurane congeners and pharmaceutical derivatives thereof.
Open Research
Data Availability Statement
The data that support the findings of this study are available in the Supporting Information of this article.
Supporting Information
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| anie202305516-sup-0001-compound19.cif328.1 KB | Supporting Information |
| anie202305516-sup-0001-compound42.cif341.8 KB | Supporting Information |
| anie202305516-sup-0001-compound47.cif1.4 MB | Supporting Information |
| anie202305516-sup-0001-misc_information.pdf4.5 MB | Supporting Information |
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