Interception and Synthetic Application of Diradical and Diene Forms of Dual-Nature Azabicyclic o-Quinodimethanes Generated by 6π-Azaelectrocyclization

Majji Shankar, Daniel J. Lee, Supuni I.N.Hewa Inaththappulige, Ayush Acharya, Hemant P. Yennawar, Ramesh Giri

Research output: Contribution to journalArticlepeer-review

Abstract

We demonstrate that 2-alkenylarylaldimines and ketimines undergo thermal 6π-azaelectrocyclization to generate a wide range of azabicyclic o-quinodimethanes (o-QDMs). These o-QDMs exist as a hybrid of a diene and a benzylic diradical. The diradical nature was confirmed by their ability to undergo dimerization and react with H-atom donor, 2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) and O2. In addition, the interception of the diradicaloid o-QDMs by H-atom transfer was used to synthesize five tetrahydroisoquinoline alkaloids and related bioactive molecules. The diene form can undergo [4+2] cycloaddition reactions with different dienophiles to generate bridged azabicycles in high endo:exo selectivity. The azabicyclic o-QDMs can be generated for [4+2] cycloaddition from a wide range of electronically and sterically varied 2-alkenylarylimines, including mono, di, tri and tetrasubstituted alkenes, and imines derived from arylamine, alkylamine (1°, 2°, 3°), benzylamine, benzylsulfonamide and Boc-amine.

Original languageEnglish (US)
Article numbere202409613
JournalAngewandte Chemie - International Edition
Volume63
Issue number41
DOIs
StatePublished - Oct 7 2024

All Science Journal Classification (ASJC) codes

  • Catalysis
  • General Chemistry

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