Interception and Synthetic Application of Diradical and Diene Forms of Dual-Nature Azabicyclic o-Quinodimethanes Generated by 6p-Azaelectrocyclization.
Angew Chem Int Ed Engl
; : e202409613, 2024 Jul 18.
Article
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| MEDLINE
| ID: mdl-39024419
ABSTRACT
We demonstrate that 2-alkenylarylaldimines and ketimines undergo thermal 6p-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 endoexo 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.
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1
Colección:
01-internacional
Base de datos:
MEDLINE
Idioma:
En
Revista:
Angew Chem Int Ed Engl
Año:
2024
Tipo del documento:
Article
País de afiliación:
Estados Unidos
Pais de publicación:
Alemania