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Remote Editing of Stacked Aromatic Assemblies for Heteroannular C−H Functionalization by a Palladium Switch between Aromatic Rings.
- Source :
- Angewandte Chemie International Edition; 11/25/2022, Vol. 61 Issue 48, p1-10, 10p
- Publication Year :
- 2022
-
Abstract
- An approach allowing remote editing of stacked aromatic assemblies for heteroannular C−H functionalization would represent a transformative chemical toolbox that may make the diversification of complex molecules in a straightforward manner. However, such a C−H activation is usually less kinetically and thermodynamically favorable than homoannular ortho C−H activation and remains a fundamental challenge. Herein we disclose an engineer's approach, using a transient ligand as an interim bridge between two aryl rings (analogues to mountaintops) to anchor the metal center on the remote heteroannular C−H bond. As a proof‐of‐concept, we present the palladium‐catalyzed heteroannular C−H olefination of stacked aromatic assemblies with olefins and allylation with vinyl acetates using L‐tert‐leucine acid as a transient ligand. Mechanistic investigations suggest an unusual olefin coordination‐promoted interannular palladium migration process determinative for reversal of the site‐selectivity. [ABSTRACT FROM AUTHOR]
- Subjects :
- PALLADIUM
ENGINEERS
ALKENES
ALLYLATION
VINYL acetate
Subjects
Details
- Language :
- English
- ISSN :
- 14337851
- Volume :
- 61
- Issue :
- 48
- Database :
- Complementary Index
- Journal :
- Angewandte Chemie International Edition
- Publication Type :
- Academic Journal
- Accession number :
- 160305873
- Full Text :
- https://doi.org/10.1002/anie.202212079