Acceleration of Inward Ring Opening of 3-Phosphorylcyclobutenes
Acceleration of Inward Ring Opening of 3-Phosphorylcyclobutenes
复制标题
3-磷酰环丁烯的向内开环加速
DOI：
10.1002/ajoc.201600585
复制
发表时间：
2017
影响因子：
2.7
通讯作者：
and Masahiro Murakami
中科院分区：
文献类型：
--
作者：
Naoki Ishida;Takaaki Yano;and Masahiro Murakami
3-磷酰基环丁烯比环丁烯本身更快地进行4π-电环开环反应，并以异构体为主得到相应的1，3-二烯。膦酸酯取代基的加速效应和向内优先性归因于环丁烯骨架的断裂C-C σ-轨道与过渡态的P-O σ* 轨道之间的轨道相互作用。
3‐Phosphorylcyclobutenes undergo a 4π‐electrocyclic ring opening reaction faster than cyclobutene itself, and afford the corresponding 1,3‐dienes with thecisisomer predominating. The accelerating effect and the inward preference of the phosphonate substituents are ascribed to the orbital interaction between the breaking C−C σ‐orbital of the cyclobutene backbone with the P−O σ* orbitals at the transition state.