| Title | Reversible C-N Bond Formation in the Zirconium-Catalyzed Intermolecular Hydroamination of 2-Vinylpyridine |
| Publication Type | Journal Article |
| Year of Publication | 2019 |
| Authors | Griffin, SE, Pacheco, J, Schafer, LL |
| Journal | Organometallics |
| Volume | 38 |
| Pagination | 1011-1016 |
| Date Published | 02/2019 |
| ISSN | 0276-7333 |
| 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. |
| DOI | 10.1021/acs.organomet.8b00904 |
