Stereoelectronic factors in bridgehead C-H bond insertion: Studies toward the total synthesis of maoecrystal v

Santa Jansone-Popova, Jeremy A. May

Research output: Contribution to journalArticlepeer-review

17 Scopus citations

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 languageEnglish
Pages (from-to)3734-3747
Number of pages14
JournalTetrahedron
Volume72
Issue number26
DOIs
StatePublished - 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

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