Intra- versus Intermolecular Carbon-to-Carbon Proton Transfers in the Reactions of Arynes with Nitrogen Nucleophiles: A DFT Study

摘要

Carbon-to-carbon proton transfer (PT) is an elementary reaction in organic chemistry. Herein we report a systematic DFT study on the carbon-to-carbon proton transfers in the reactions of arynes with nitrogen nucleophiles, including tertiary amines, aziridines, imines, and N -heteroarenes. DFT calculations indicated that the Gibbs energies of activation for the 1,4- and 1,5-proton transfers involved are lower than 20 kcal/mol in most cases. We also found that the Bell–Evans–Polanyi principle applies to the 1,4-proton transfers, indicating that the more exergonic an intramolecular proton transfer is (the more stable a carbanion is generated), the faster it will be. Previous experimental studies have shown that, in the presence of a carbon nucleophile (NuH; e.g., CHCl_(3) and MeCN) as the third component (also as the solvent), intermolecular proton abstractions may compete with the intramolecular proton transfers and lead to different products. Our theoretical rationalization of these competitions is that the introduction of an electron-withdrawing group at the acidic site can accelerate the intramolecular proton transfer dramatically (owing to the generation of a more stable carbanion), making it compete with the intermolecular processes. In addition, we have also discussed the competition between intra- and intermolecular proton transfers when NuH is used as the reactant rather than the solvent.