Pinku Prasad Mondal, Sourav Das, Aarya Mandodi, Preeti Christina Beck, Debdutta Chakraborty, Basudev Sahoo
Nucleophilic alkylation of gem -dichlorocyclobutenones with alkyl-organometallics is relatively challenging in accessing C(sp 3 )-enriched α-chlorocyclobutenones. Leveraging single-electron oxidation ability, herein, we report readily accessible alkyltrifluoroborates, enabling a photoinduced SOMOphilic allylic alkylation of gem -dichlorocyclobutenones under metal-free conditions. Additionally, alkene feedstocks are exploited as latent C(sp 3 ) partners in this C(sp 3 )–C(sp 3 ) bond-forming transformation. This reaction proceeds with high fidelity, expanding the previously limited scope of β-alkyl cyclobutenones beyond β-aryl analogues and enabling access to pharmaceutically relevant scaffolds. Conceptual DFT calculations rationalize the preferential α-radical addition over β-addition, alongside other experimental supports, including an EPR study, for the SET-mediated mechanism.