Abstract
A strategy for the total synthesis of maoecrystal V is presented. The key interior vicinal quaternary carbon centers will be formed via sequential bridgehead C-H bond insertion and enolate functionalization. Studies herein validate the C-H bond insertion as feasible in model studies, though there are significant effects on the selectivity for the bridgehead position from neighboring groups. Both inductive electron withdrawing elements and sterics play a role in deactivating that position, with the former having a greater effect. Forming the second quaternary carbon is possible via enolate acylation and alkylation. Lastly, an approach to synthesize the cyclohexenone ring of maoecrystal V is described.
Original language | English |
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Pages (from-to) | 3734-3747 |
Number of pages | 14 |
Journal | Tetrahedron |
Volume | 72 |
Issue number | 26 |
DOIs | |
State | Published - Jun 30 2016 |
Funding
The authors wish to thank the Welch Foundation (grant E-1744 ) and NSF (grant CHE-1352439 ) for financial support of this effort. Dr. Ilja Popovs is thanked for helpful discussions.
Keywords
- C-H activation
- C-H bond insertion
- Carbenes
- Maoecrystal V
- Stereoelectronic effects