Asymmetric Total Synthesis of Dankasterones A and B and Periconiastone A Through Radical Cyclization
Pengquan Chen1, Cheng Wang1, Rui Yang1
1Key Lab of Functional Molecular Engineering of Guangdong Province, School of Chemistry & Chemical Engineering, South China University of Technology, Wushan Road-381, Guangzhou, 510641, China.
Abstract:
We describe herein the assembly of the cis-decalin framework through radical cyclization initiated by metal-catalyzed hydrogen atom transfer (MHAT), further applied it in the asymmetric synthesis of dankasterones A and B and periconiastone A. Position-selective C-H oxygenation allowed for installation of the necessary functionality. A radical rearrangement was adopted to create 13(14→8)abeo-8-ergostane skeleton. Interconversion of dankasterone B and periconiastone A was realized through biomimetic intramolecular aldol and retro-aldol reactions. The MHAT-based approach, serves as a new dissection means, is complementary to the conventional ways to establish cis-decalin framework.
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