Carbene-enabled ether activation through the formation of oxonium: a theoretical view

Here, we report a theoretical investigation of the reactivity and chemoselectivity of carbene-enabled ether activation. The mechanism obtained from DFT calculations revealed that the final products were dependent on the stability of the oxonium intermediate, which was afforded by nucleophilic attack of the corresponding ether onto a carbene species. Interestingly, we found that the nucleophilicity of ethers was crucial but not their solvation. Energy decomposition analysis based on absolutely localized molecular orbitals showed that the nucleophilicity of ethers was critical for polarization and charge transfer, leading to the chemoselectivity.

Automated summary

Theoretical investigation of carbene-enabled ether activation revealed that the final products were dependent on the stability of the oxonium intermediate, achieved through nucleophilic attack of ethers onto carbene species. The nucleophilicity of ethers was found to be crucial for polarization and charge transfer, influencing the chemoselectivity of the reaction. Surprisingly, solvation of ethers did not play a significant role in determining the outcome of the reaction.