Exploiting the (-C-H···C-) Interaction to Design Cage-Functionalized Organic Superbases and Hyperbases: A Computational Study.

A set of carbon center-based P-ylidesubstituting bases have been exploited computationally with pentacyclo[5.4.0.0 2,6 .0 3,10 .0 5.9 ]undecane (PCU) and pentacyclo [6.4.0.0 2,7 .0 3,11 .0 6,10 ] dodecane (PCD) scaffolds using the B3LYP-D3/6-311+G(d,p) level of theory. The proton affinities calculated in the gas phase are in the range of superbases and hyperbases. The Atomsin-Molecules and Natural Bond Orbital calculations reveal that the -C-H···C- interaction plays a substantial role in improving the basicity, and tuning the -C-H···C- interaction can enhance the basicity of such systems. The free activation energy for proton exchange for PCD and PCU scaffolds substituted with P-ylide is substantially low. The computed results reveal the strength and nature of such - C-H···C- interactions compared to the -N-H···N- hydrogen bonds. The isodesmic reactions suggest that the superbasicity achieved using these frameworks arises from a combination of several factors, such as the ring strain of the bases in their unprotonated form, steric repulsion, and the intramolecular -C-H···C- interaction.