Ti-catalyzed ring-opening oxidative amination of methylenecyclopropanes with diazenes
| Autor: | Ian A. Tonks, Jason D. Goodpaster, Evan P. Beaumier, Amy A. Ott, Zachary W. Davis-Gilbert, Xuelan Wen, T. Alexander Wheeler, Joseph J. Topczewski |
|---|---|
| Rok vydání: | 2020 |
| Předmět: |
chemistry.chemical_classification
Ketone Imine chemistry.chemical_element Regioselectivity Oxidative phosphorylation General Chemistry Metallacycle Methylenecyclopropane Ring (chemistry) Medicinal chemistry Catalysis Chemistry chemistry.chemical_compound chemistry Polymer chemistry Density functional theory Amination Titanium |
| Zdroj: | Chemical Science |
| ISSN: | 2041-6539 2041-6520 |
| DOI: | 10.1039/d0sc01998d |
| Popis: | The ring-opening oxidative amination of methylenecyclopropanes (MCPs) with diazenes catalyzed by py3TiCl2(NR) complexes is reported. This reaction selectively generates branched α-methylene imines as opposed to linear α,β-unsaturated imines, which are difficult to access via other methods. Products can be isolated as the imine or hydrolyzed to the corresponding ketone in good yields. Mechanistic investigation via density functional theory suggests that the regioselectivity of these products results from a Curtin–Hammett kinetic scenario, where reversible β-carbon elimination of a spirocyclic [2 + 2] azatitanacyclobutene intermediate is followed by selectivity-determining β-hydrogen elimination of the resulting metallacycle. Further functionalizations of these branched α-methylene imine products are explored, demonstrating their utility as building blocks. The ring-opening oxidative amination of methylenecyclopropanes (MCPs) with diazenes catalyzed by py3TiCl2(NR) complexes is reported. |
| Databáze: | OpenAIRE |
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