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Vinylogous anionic processes in the formation and interconversion of tetracyclic ring systems
Paul D Thornton1, T Stanley Cameron, D Jean Burnell
1Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, Canada B3H 4J3.
Tricyclic vinyl enones were converted into fused tetracycles using tandem reactions. Subsequent skeletal reorganization of tetracyclic products occurred via ring-opening and varied ring-closure pathways under basic conditions.
Area of Science:
- Organic Chemistry
- Synthetic Chemistry
Background:
- Tricyclic vinyl enones are versatile precursors in organic synthesis.
- Tandem reactions offer efficient pathways to complex molecular architectures.
Purpose of the Study:
- To investigate the transformation of tricyclic vinyl enones into fused tetracycles.
- To explore the skeletal reorganization of tetracyclic products under basic conditions.
Main Methods:
- Tandem oxy-Cope and vinylogous aldol reactions.
- Vinylogous retro-aldol, conjugate addition, and vinylogous aldol reactions.
- Treatment of tetracyclic mesylates with tert-butoxide.
Main Results:
- Tricyclic vinyl enones were successfully converted into fused tetracycles.
- Tetracyclic products underwent skeletal reorganization via transannular ring-opening.
- Different modes of transannular ring-closure were observed upon treatment with tert-butoxide.
Conclusions:
- Tandem reactions provide a viable route to complex fused tetracycles.
- The skeletal reorganization of tetracyclic systems is sensitive to reaction conditions, leading to diverse outcomes.
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