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Reversible C-N Bond Formation in the Zirconium-Catalyzed Intermolecular Hydroamination of 2-Vinylpyridine

TitleReversible C-N Bond Formation in the Zirconium-Catalyzed Intermolecular Hydroamination of 2-Vinylpyridine
Publication TypeJournal Article
Year of Publication2019
AuthorsGriffin, SE, Pacheco, J, Schafer, LL
JournalORGANOMETALLICS
Volume38
Pagination1011-1016
Date PublishedMAR 11
ISSN0276-7333
Abstract

The intermolecular hydroamination of alkenes with alkylamines has been a long-standing challenge in catalysis, partially due to the near-thermoneutral nature of this transformation. Consistent with this understanding, we report the direct observation of reversible C-N bond formation in hydroamination. A bis(ureate) zirconium complex catalyzed the intermolecular hydroamination of 2-vinylpyridine. Reversible C-N bond formation was characterized by variable-temperature NMR spectroscopy, and thermodynamic parameters were determined using van't Hoff plots. Isolated intermediates support an aza-Michaeladdition mechanism. Sensitivity to steric bulk in the C-N bond forming step provided further evidence for the kinetically accessible but limited thermodynamic driving force for this transformation.

DOI10.1021/acs.organomet.8b00904