A Rapid Aza-Bicycle Synthesis from Dendralenes and Imines

Yi Min Fan, Josemon George, Jiao Yu J. Wang, Michael G. Gardiner, Michelle L. Coote, Michael S. Sherburn

Research output: Contribution to journalArticlepeer-review

1 Citation (Scopus)

Abstract

The diene-transmissive 2-fold Diels-Alder sequence between carbon-based dienophiles and [3]dendralenes is becoming an established method for polycarbocycle synthesis. Here, we demonstrate for the first time that imines are competent participants in intermolecular formal [4 + 2] cycloadditions with dendralenes. After a second Diels-Alder process with a carbadienophile, hexahydro- and octahydro-isoquinoline structures are formed. The formal aza-Diels-Alder reaction, which requires Lewis acid promotion, proceeds in high regio- and stereoselectivity under optimized conditions. ωB97XD/Def2-TZVP//M06-2X/6-31+G(d,p) calculations reveal a stepwise ionic mechanism for the formal aza-dienophile cycloadditions and also explain an unexpected Z → E olefin isomerization of a non-reacting C═C bond in the first formal cycloaddition.

Original languageEnglish
Pages (from-to)7545-7550
Number of pages6
JournalOrganic letters
Volume25
Issue number41
DOIs
Publication statusPublished - 20 Oct 2023

Keywords

  • Aza-Bicycle Synthesis
  • Dendralenes
  • Imines
  • diene-transmissive
  • Diels-Alder
  • Carbon-based polymer composites
  • dienophiles
  • polycarbocycle synthesis

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