Mild C–C Bond Formation via Lewis Acid Catalyzed Oxetane Ring Opening with Soft Carbon Nucleophiles

Abstract Mild oxetane opening by soft carbon nucleophiles has been developed for efficient C−C bond formation. In the presence of LiNTf 2 or TBSNTf 2 as catalyst, silyl ketene acetals were found to be effective nucleophiles to generate a wide range of highly oxygenated molecules, which are key substructure in natural products like polyketides. Furthermore, intramolecular oxetane opening by a styrene‐based carbon nucleophile via a Prins‐type process was also achieved with Sc(OTf) 3 as catalyst, leading to efficient formation of the useful 2,3‐dihydrobenzo[b]oxepine skeleton.