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

Autor: Shankar M; Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania, 16802, United States., Lee DJ; Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania, 16802, United States., Inaththappulige SINH; Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania, 16802, United States., Acharya A; Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania, 16802, United States., Yennawar HP; Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania, 16802, United States., Giri R; Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania, 16802, United States.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Oct 07; Vol. 63 (41), pp. e202409613. Date of Electronic Publication: 2024 Sep 05.
DOI: 10.1002/anie.202409613
Abstrakt: 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 O 2 . 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.
(© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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