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Updated: Dec 12, 2025

Spatial Separation of Molecular Conformers and Clusters
Published on: January 9, 2014
Diversification of Nucleophile-Intercepted Beckmann Fragmentation Products and Related Density Functional Theory
Leah L Lowder1, Fengyue Zhao2, Mathes M Vaughan1
1Department of Chemistry, Dartmouth College, Hanover, New Hampshire 03755, United States.
Abstract:
The nucleophile-intercepted Beckmann fragmentation (NuBFr) has the potential to be broadly applicable to the synthesis of indoline alkaloid-based natural products. However, the reaction has not been widely adopted, in part, because of limitations associated with the availability of appropriate promoter-Nu reagents. We have devised a stereospecific Ag(I)-promoted reaction for functionalizing NuBFr products to give novel compositions of matter that may be useful in synthesis and medicinal chemistry. With unhindered amine nucleophiles, structurally unique [2.2.2]-bicycloamidines are generated. We also disclose for the first time detailed density functional theory studies, which shed light on the mechanism of the NuBFr and Ag-promoted substitution reaction that supports an unusual aziridinium ion as a key intermediate.
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