Palladium-catalysed C-H bond zincation of arenes: scope, mechanism, and the role of heterometallic intermediates
File(s)_CHZincation-ACIE-3Dec.pdf (2.34 MB)
Accepted version
Author(s)
Garçon, Martí
Mun, Nicolette Wee
White, Andrew JP
Crimmin, Mark R
Type
Journal Article
Abstract
Catalytic methods that transform C-H bonds into C-X bonds are of paramount importance in synthesis. A particular focus has been the generation of organoboranes, organosilanes and organostannanes from simple hydrocarbons (X=B, Si, Sn). Despite the importance of organozinc compounds (X=Zn), their synthesis by the catalytic functionalisation of C-H bonds remains unknown. Herein, we show that a palladium catalyst and zinc hydride reagent can be used to transform C-H bonds into C-Zn bonds. The new catalytic C-H zincation protocol has been applied to a variety of arenes-including fluoroarenes, heteroarenes, and benzene-with high chemo- and regioselectivity. A mechanistic study shows that heterometallic Pd-Zn complexes play a key role in catalysis. The conclusions of this work are twofold; the first is that valuable organozinc compounds are finally accessible by catalytic C-H functionalisation, the second is that heterometallic complexes are intimately involved in bond-making and bond-breaking steps of C-H functionalisation.
Date Issued
2021-03-08
Date Acceptance
2020-12-04
Citation
Angewandte Chemie International Edition, 2021, 60 (11), pp.6145-6153
ISSN
1433-7851
Publisher
Wiley
Start Page
6145
End Page
6153
Journal / Book Title
Angewandte Chemie International Edition
Volume
60
Issue
11
Copyright Statement
© 2020 Wiley‐VCH GmbH. This is the peer reviewed version of the following article, which has been published in final form at https://onlinelibrary.wiley.com/doi/10.1002/anie.202014960. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.
Sponsor
Commission of the European Communities
Identifier
https://www.ncbi.nlm.nih.gov/pubmed/33275830
Grant Number
677367
Subjects
C−H activation
C−H zincation
heterometallics
mechanism
palladium
Publication Status
Published
Coverage Spatial
Germany
Date Publish Online
2020-12-04