Low-Temperature Intramolecular [4+2] Cycloaddition of Allenes with Arenes for the Synthesis of Diene Ligands.
Angew Chem Int Ed Engl
; 60(10): 5475-5481, 2021 Mar 01.
Article
em En
| MEDLINE
| ID: mdl-33216417
ABSTRACT
The intramolecular [4+2] cycloaddition between arenes and allenes first reported by Himbert gives rapid access to rigid polycyclic scaffolds. Herein, we report a one-pot oxyalkynylation/cycloaddition reaction proceeding under mild conditions (23-90 °C) and providing complex polycyclic architectures with high efficiency, and atom and step economy. The bicyclo[2.2.2]octadiene products were obtained with a wide variety of useful functional groups and were successfully applied as chiral ligands for metal catalysis. Computational studies gave a first rationalization of the low activation energy for the cycloaddition based on counter-intuitive favorable dispersive interactions in the transition state.
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MEDLINE
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En
Ano de publicação:
2021
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Article