Synthesis of 2-Quinuclidonium by Eliminating Water: Experimental Quantification of the High Basicity of Extremely Twisted Amides
The chemical properties of an extremely twisted amide are examined quantitatively for the first time. The predicted high basicity of 2-quinuclidonium is confirmed experimentally by measuring the gas-phase proton affinity using the extended kinetic method. Fragmentation of this molecule further reveals that the lack of resonance stabilization weakens the amide bond. Furthermore, a new route for synthesizing 2-quinuclidonium by eliminating water is demonstrated in the gas phase.
Additional Information© 2007 American Chemical Society. Received 27 October 2006. Published online 27 January 2007. Published in print 1 February 2007. We acknowledge funding from the University of California, Riverside, Ono Pharmaceutical Co. Ltd (for a postdoctoral fellowship to K.T.), and Bristol-Myers Squibb. D.K.P. thanks the Kenan Trust and the NSF REU Site in Bioanalytical Science supported by Grant CHE-0552493.
Supplemental Material - ja067703msi20070118_030344.pdf