Utilizing primary amines as alkyl coupling partners has garnered attention in recent years due to their widespread availability, facile preparation and purification, and presence in a variety of common building blocks. The reemergence of Katritzky salts has enabled deaminative alkylation and arylation of alpha primary and alpha secondary amines.
The Rovis group has developed deaminative conditions for alpha tertiary amines utilizing redox-active imines to generate tertiary carbon-centered radicals. Herein, we couple this tertiary alkyl radical to haloarenes to generate benzylic quaternary centers, a common motif in pharmaceuticals and natural products.
We then applied this methodology in the realm of isotopic exchange to generate 15N-primary amines from their naturally occurring 14N-analogues. By activating alpha primary and alpha secondary amines to Katritzky pyridinium salts and alpha tertiary amines to redox-active imines, we can engage primary alkyl amines in a late-stage isotopic exchange with complete and selective isotopic labeling.
| Identifer | oai:union.ndltd.org:columbia.edu/oai:academiccommons.columbia.edu:10.7916/vxpx-k515 |
| Date | January 2024 |
| Creators | Dorsheimer, Julia Reid |
| Source Sets | Columbia University |
| Language | English |
| Detected Language | English |
| Type | Theses |
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