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Carbon Atom Deletion Strategy Enabled Synthesis of 22-epi-6-Deoxocastasterone Using the Intact Skeleton of Tigogenin
Zhi-Hao Shang1, Xiaotong Li1, Dihua Yan1
1State Key Laboratory of Synergistic Chem-Bio Synthesis, Frontiers Science Center for Transformative Molecules, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Zhangjiang Institute for Advanced Study, Shanghai Jiao Tong University, Shanghai 200240, China.
Abstract:
A stepwise carbon atom deletion strategy was developed to construct the brassinosteroid-type side chain from intact steroidal sapogenins with high atom economy. Key C23 deletion via oxidation, Favorskii rearrangement, and decarboxylative borylation converted the inherent C25 chiral methyl into the target C24 methyl. Further transformations, including spiroketal ring-opening and one-pot Barton-McCombie deoxygenation, enabled the efficient synthesis of a non-natural analogue, 22-epi-6-deoxocastasterone, offering a novel route for structural diversification.
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