Journal of Organic Chemistry
Journal of Organic Chemistry
4 years ago

Carbanion Translocations via Intramolecular Proton Transfers: A Quantum Chemical Study

Carbanion Translocations via Intramolecular Proton Transfers: A Quantum Chemical Study
Pei-Jun Cai, Yi Wang, Zhi-Xiang Yu
Intramolecular proton transfers are important processes in chemical reactions and biological transformations. In particular, the translocation of reactive carbanion centers can be achieved through 1,n-proton transfer in either a direct or an assisted manner (via the protonation/deprotonation mechanism). Despite some mechanistic investigations on proton transfers within zwitterionic species, no guiding principles have been summarized for carbanion-induced intramolecular proton transfers. Herein, we report our quantum chemical study on the carbanion translocations via intramolecular proton transfers. Our calculations indicated that the reaction barriers generally decrease with longer tether lengths and more π-withdrawing substituents. The physical bases behind these effects were revealed according to the charge and bond energy decomposition analysis, showing that the destabilizing closed-shell Pauli repulsions play important roles in determining the relative ease of intramolecular proton transfers. We also found that the thermodynamic driving force may affect the regiochemistry. This study may help chemists to understand whether a carbanion translocation occurs via an intramolecular proton transfer or with the assistance of proton shuttles, such as water and alcohols.

Publisher URL: http://dx.doi.org/10.1021/acs.joc.7b00194

DOI: 10.1021/acs.joc.7b00194

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