科研之友
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摘要
Regioselectivity of Diels-Alder reaction of the anti-Bredt olefin of fulleroid, the 5,6-methylene-bridged fullerene derivative, is theoretically clarified by DFT calculations. In transition state calculations, the addition of a noncyclic diene 2,3-dimethyl-1,3-butadiene (DMBD) at the anti-Bredt olefin has considerably lower activation energy than those at the other sixteen olefins, while the reaction of a rigid cyclic diene cyclohexadiene (CHD) has similar activation energy at both anti-Bredt and another nontwisted olefin. The changes in strain and interaction of the reactants are estimated along its reaction coordinate by activation strain model. Noncyclic diene shows asynchronous C-C bond formation with a significant gain of interaction energy, while the rigid cyclic diene shows a large growth of strain energy canceling out the interaction energy between diene and fulleroid.
- 出版日期2017-12-5
