Pavošević Fabijan, Smith Robert L, Rubio Angel
Center for Computational Quantum Physics, Flatiron Institute, 162 Fifth Avenue, New York, New York 10010, United States.
Algorithmiq Ltd, Kanavakatu 3C, FI-00160 Helsinki, Finland.
J Phys Chem A. 2023 Dec 7;127(48):10184-10188. doi: 10.1021/acs.jpca.3c06285. Epub 2023 Nov 22.
Click chemistry, which refers to chemical reactions that are fast and selective with high product yields, has become a powerful approach in organic synthesis and chemical biology. Due to the cytotoxicity of the transition metals employed in click chemistry reactions, a search for novel metal-free alternatives continues. Herein, we demonstrate that an optical cavity can be utilized as a metal-free alternative in the click chemistry cycloaddition reaction between cyanoacetylene and formylazide using the quantum electrodynamics coupled cluster method. We show that by changing the molecular orientation with respect to the polarization of the cavity mode(s), the reaction can be selectively catalyzed to form a major 1,4-disubstituted or 1,5-disubstituted product. This work highlights that a cavity has the same effect on the investigated cycloaddition as the transition metal catalysts traditionally employed in click chemistry reactions. We expect our findings to further stimulate research on cavity-assisted click chemistry reactions.
点击化学是指具有快速、选择性且产物收率高的化学反应，已成为有机合成和化学生物学中的一种强大方法。由于点击化学反应中使用的过渡金属具有细胞毒性，因此对新型无金属替代物的探索仍在继续。在此，我们证明了利用量子电动力学耦合簇方法，光学腔可以作为氰基乙炔和甲酰叠氮化物之间点击化学环加成反应的无金属替代物。我们表明，通过改变分子相对于腔模极化的取向，可以选择性地催化反应，形成主要的1,4-二取代或1,5-二取代产物。这项工作突出了腔对所研究的环加成反应具有与传统点击化学反应中使用的过渡金属催化剂相同的效果。我们期望我们的发现能进一步激发对腔辅助点击化学反应的研究。
