Mechanistic Insights into Iron-Catalyzed C–H Bond Activation and C–C Coupling

Authors

• Samantha M. Brewer, Texas Christian University
• Timothy M. Schwartz, Texas Christian University
• Magy A. Mekhail, Chapman UniversityFollow
• Lara S. Turan, Texas Christian University
• Timothy J. Prior, University of Hull
• Timothy J. Hubin, Southwestern Oklahoma State University
• Benjamin G. Janesko, Texas Christian University
• Kayla N. Green, Texas Christian University

Document Type

Article

Publication Date

7-20-2021

Abstract

Iron-catalyzed C–C coupling reactions of pyrrole provide a unique alternative to the traditional Pd-catalyzed counterpart. However, many details regarding the actual mechanism remain unknown. A series of macrocyclic iron(III) complexes were used to evaluate specifics related to the role of O₂, radicals, and μ-oxodiiron-complex participation in the catalytic cycle. It was determined that the mononuclear tetra-azamacrocyclic complex is a true catalyst and not a stoichiometric reagent, while more than one equivalent of a sacrificial oxidant is needed. Furthermore, the reaction does not proceed through an organic radical pathway. μ-Oxodiiron complexes are not involved in the main catalytic pathway, and the dimers are, in fact, off-cycle species that decrease catalytic efficiency.

Comments

This is a pre-copy-editing, author-produced PDF of an article accepted for publication in Organometallics, volume 40, issue 15, in 2021 following peer review. This article may not exactly replicate the final published version. The definitive publisher-authenticated version is available online at https://doi.org/10.1021/acs.organomet.1c00211.

Recommended Citation

Brewer, S. M.; Schwartz, T. M.; Mekhail, M. A.; Turan, L.; Prior, T. J.; Hubin, T. J., Green, K. N. Mechanistic insight into iron-catalyzed Suzuki-Miyaura type C-C coupling. Organometallics 2021, 40(15), 2467-2477. https://doi.org/10.1021/acs.organomet.1c00211

Copyright

Royal Society of Chemistry