4.8 Article

Remote Editing of Stacked Aromatic Assemblies for Heteroannular C-H Functionalization by a Palladium Switch between Aromatic Rings

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 61, Issue 48, Pages -

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202212079

Keywords

C-H Functionalization; Ferrocenes; Olefination; Palladium Catalysis; Transient Directing Group

Funding

  1. National Key R&D Program of China [2021YFA1500100]
  2. National Natural Science Foundation of China (NSFC) [22031007, 22171188]

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In this study, we present a new approach allowing remote editing of stacked aromatic assemblies through the use of a transient ligand as a bridge. Our results demonstrate the successful heteroannular C-H functionalization and uncover a unique reaction mechanism involving olefin coordination.
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.

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