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

Anusuya Saha; Bishwajit Ganguly

doi:10.1021/acsomega.3c05401

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

ACS Omega. 2023 Oct 2;8(41):38546-38556. doi: 10.1021/acsomega.3c05401. eCollection 2023 Oct 17.

Authors

Anusuya Saha^{1

2}, Bishwajit Ganguly^{1

2}

Affiliations

¹ Computation and Simulation Unit, Analytical and Environmental Science Division and Centralized Instrument Facility, CSIR-Central Salt & Marine Chemicals Research Institute, Bhavnagar, Gujarat 364002, India.
² Academy of Scientific and Innovative Research (AcSIR), Ghaziabad 201002, India.

Abstract

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.