Huang Shuangping, Ma Jing, Yi Yikun, Li Mingtao, Cai Ping, Wu Na
College of Biomedical Engineering, Taiyuan University of Technology, Taiyuan, Shanxi, 030024, China.
School of Chemical Engineering and Technology, Xi'an Jiaotong University, Xi'an, Shann'xi, 710049, China.
Org Biomol Chem. 2022 May 26;20(20):4081-4085. doi: 10.1039/d2ob00677d.
Herein, we report a catalyst-free 'click' reaction: metal-free [2 + 2] cycloaddition-retro-electrocyclisation (CA-RE) of arylynamines with the sluggish acceptor tetracyanoquinodimethane (TCNQ) to provide orthogonal electron-push-pull light-harvesting small molecules: N-heterocyclic dicyanoquinodimethane-substituted methylene malononitriles. Ynamines are reactive alkynes and tend to induce over-reactions with the CA-RE adducts. The reactivity of arylynamines was balanced properly by ensuring the electron-density of the nitrogen atom was delocalised more over the aromatic rings than the triple bond.
在此，我们报道了一种无催化剂的“点击”反应：芳基炔胺与惰性受体四氰基对苯二醌二甲烷（TCNQ）的无金属[2 + 2]环加成-逆电环化反应（CA-RE），以提供正交的电子推-拉光捕获小分子：N-杂环二氰基对苯二醌二甲烷取代的亚甲基丙二腈。炔胺是活性炔烃，容易与CA-RE加合物发生过度反应。通过确保氮原子的电子密度在芳环上的离域程度高于三键，适当平衡了芳基炔胺的反应活性。
