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-pi 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.
The effect of tethered bi-naphthyls on visible-light promoted alkene-alkene [2 + 2] cycloadditions / Hoch, Matteo; Sparascio, Sara; Cerveri, Alessandro; Bigi, Franca; Maggi, Raimondo; Viscardi, Rosanna; Maestri, Giovanni. - In: PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES. - ISSN 1474-905X. - (2024). [10.1007/s43630-024-00615-5]
The effect of tethered bi-naphthyls on visible-light promoted alkene-alkene [2 + 2] cycloadditions
Hoch, Matteo;Sparascio, Sara;Cerveri, Alessandro;Bigi, Franca;Maggi, Raimondo;Maestri, Giovanni
2024-01-01
Abstract
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-pi 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.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.