Hoch Matteo, Sparascio Sara, Cerveri Alessandro, Bigi Franca, Maggi Raimondo, Viscardi Rosanna, Maestri Giovanni
Department of Chemistry, Life Sciences and Environmental Sustainability, Università di Parma, Parco Area delle Scienze 17/A, 43124, Parma, Italy.
IMEM-CNR, Parco Area delle Scienze 37/A, 43124, Parma, Italy.
Photochem Photobiol Sci. 2024 Aug;23(8):1543-1563. doi: 10.1007/s43630-024-00615-5. Epub 2024 Jul 29.
Dispersion interactions are ubiquitous weak interactions that can play a role in many chemical events. Tailor-made catalysts and additives can lead to more selective reactions by properly exploiting dispersion interactions. Although radical-π dispersion interactions are known to have an important stabilizing role, this concept has been so far overlooked in synthetic photochemistry. We recently proved that similar dispersion interactions can play a profound impact on several reactions involving an energy transfer step. We present herein a study on the co-catalytic effect of tethered bi-naphthyl derivatives on the visible-light-promoted alkene-alkene [2 + 2] cycloaddition. A library of tethered bi-naphthyl derivatives was prepared in order to evaluate the impact of the tether on the efficiency of the prototypical [2 + 2] cycloaddition. The best performing additives showed a dramatic effect on the efficiency of the cyclization, and a rationalization of their relative efficiency was carried out through DFT modeling. The best co-catalyst allowed one to isolate desired products in good to excellent yields even employing several challenging substrates. These results offer new tools to devise optimized [2 + 2] photocycloaddition methods and provide valuable information for the design of organic co-catalyst that can boost photochemical reactions by exploiting dispersion interactions.
色散相互作用是普遍存在的弱相互作用，可在许多化学过程中发挥作用。量身定制的催化剂和添加剂可以通过合理利用色散相互作用导致更具选择性的反应。尽管已知自由基-π色散相互作用具有重要的稳定作用，但到目前为止，这一概念在合成光化学中一直被忽视。我们最近证明，类似的色散相互作用可以对涉及能量转移步骤的几个反应产生深远影响。我们在此展示了一项关于 tethered 联萘衍生物对可见光促进的烯烃-烯烃[2 + 2]环加成反应的共催化作用的研究。制备了一系列 tethered 联萘衍生物库，以评估连接基团对典型[2 + 2]环加成反应效率的影响。性能最佳的添加剂对环化效率产生了显著影响，并通过密度泛函理论（DFT）建模对它们的相对效率进行了合理化分析。即使使用几种具有挑战性的底物，最佳共催化剂也能使所需产物以良好至优异的产率分离出来。这些结果为设计优化的[2 + 2]光环加成方法提供了新工具，并为通过利用色散相互作用促进光化学反应的有机共催化剂设计提供了有价值的信息。
