Photocatalysis Enables Cross-Electrophile Coupling of Unactivated Ketones with Isothiocyanates.

The cross-electrophile coupling of unactivated ketones constitutes a persistent and considerable challenge in organic synthesis. In this work, we developed a photocatalytic cross-electrophile coupling of unactivated ketones with isothiocyanates, enabling the efficient synthesis of α-hydroxy amide, hexahydrobenzofuranone, and octahydrobenzofuran scaffolds in moderate to good yields. Mechanistic studies indicate that this transformation proceeds via an aryl radical-initiated cascade reaction of ketones with isothiocyanates. This work provides a practical protocol for the cross-coupling of two challenging electrophiles and features broad functional group tolerance and operational simplicity, significantly expanding their synthetic utility in organic synthesis.