A theoretical study for the regioselective Diels-Alder reaction of 5,6-fulleroid with strained anti-Bredt olefins
A theoretical study for the regioselective Diels-Alder reaction of 5,6-fulleroid with strained anti-Bredt olefins
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5,6-富勒烯与应变反Bredt烯烃区域选择性Diels-Alder反应的理论研究
DOI：
10.1002/qua.25438
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发表时间：
2017
期刊：
影响因子：
--
通讯作者：
Naohiko Ikuma
中科院分区：
文献类型：
--
作者：
Naohiko Ikuma;Koji Nakagawa;Ken Kokubo;Takumi Oshima;Naohiko Ikuma
通过密度泛函理论（DFT）计算，阐明了富勒烯衍生物富勒烯的反Bredt烯烃Diels-Alder反应的区域选择性.在过渡态计算中，在反Bredt烯烃上添加非环状二烯2，3-二甲基-1，3-丁二烯（DMBD）的活化能比在其他16种烯烃上的活化能低得多，而刚性环状二烯环己二烯（CHD）的反应在反Bredt和另一种非扭曲烯烃上的活化能相似。采用活化应变模型估算了应变和反应物相互作用沿反应坐标沿着的变化。非环状二烯表现出异步的C → C键的形成与相互作用能的显着增益，而刚性环状二烯表现出大的增长的应变能抵消了二烯和富勒烯之间的相互作用能。
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 CC 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.