Enantioselective oxa-Diels–Alder Sequences of Dendralenes

Yi Min Fan, Li Juan Yu, Michael G. Gardiner, Michelle L. Coote, Michael S. Sherburn

Research output: Contribution to journalArticlepeer-review

4 Citations (Scopus)
28 Downloads (Pure)

Abstract

Diene-transmissive hetero-Diels–Alder sequences involving carbonyl dienophiles are reported for the first time. High enantioselectivities are achieved in the reaction of phenylglyoxal with a broad range of dendralene structures, through the optimization of a Pd2+ catalyst system. The initial catalyst-controlled enantioselective oxa-Diels–Alder (ODA) cycloaddition to a [3]dendralene generates a dihydropyran carrying a semicyclic diene. This participates in a subsequent catalyst or substrate-controlled Diels–Alder reaction to generate sp3-rich fused polycyclic systems containing both heterocycles and carbocycles. Computational investigations reveal a concerted asynchronous mechanism. π-Complexation of a diene C=C bond to Pd2+ occurs in both the pre-transition state (TS) complex and in cycloaddition TSs, controlling stereoselectivity. A formal enantioselective [4+2]cycloaddition of a CO2 dienophile is demonstrated.

Original languageEnglish
Article numbere202204872
Number of pages6
JournalAngewandte Chemie - International Edition
Volume61
Issue number39
Early online date28 Jul 2022
DOIs
Publication statusPublished - 26 Sept 2022

Keywords

  • Asymmetric Catalysis
  • Cycloadditions
  • Dendralenes
  • Domino Reactions
  • Hydrocarbons

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