1. Structure‐Unit‐Based Total Synthesis of (−)‐Sinulochmodin C.
- Author
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Zhang, Yi‐Peng, Du, Shufei, Ma, Ying, Zhan, Weixin, Chen, Wen, Yang, Xiaodong, and Zhang, Hongbin
- Subjects
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LEWIS acids , *HYDROXYLATION , *TETRAHYDROFURAN , *OXIDATION , *ASYMMETRIC synthesis , *MOIETIES (Chemistry) - Abstract
Herein we report a structure‐unit‐based asymmetric total synthesis of sinulochmodin C, a norcembranoid diterpenoid bearing a transannular strained ether bridge β‐keto tetrahydrofuran moiety. Our synthetic route features an intramolecular double Michael addition to construct stereospecifically the [7,6,5,5] tetracyclic skeleton, a vinylogous hydroxylation/oxidation procedure or a stereospecific epoxide opening/oxidation sequence to establish the γ‐keto enone intermediate, a Lewis acid/Brønsted acid mediated transannular oxa‐Michael addition to fuse the β‐keto tetrahydrofuran moiety, a Mukaiyama hydration/Pd−C hydrogenation to reverse the C1‐configuration of the isopropenyl unit, and a bioinspired transformation of sinulochmodin C into scabrolide A. [ABSTRACT FROM AUTHOR]
- Published
- 2024
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