Photochemical C(sp 3 )-H Activation for Diversity-Oriented Synthesis of 3-Functionalized Oxindoles.

Heteroatom-adjacent C(sp 3 ) radical cyclization of N -arylacrylamides provides a straightforward pathway to synthesize valuable 3-functionalized oxindoles. Traditional cyclization reactions normally require harsh conditions or transition-metal catalysts. Here, we developed a metal-free, diversity-oriented synthesis of 3-functionalized oxindoles via photochemically induced selective cleavage of C(sp 3 )-H bonds. A variety of 3-substituted oxindoles with functionalities such as ethers, polyhalogens, benzyl, and formyl groups can be obtained by a rational design. This strategy is characterized by its simple operation and mild conditions, aligning well with the developmental requirements for sustainable chemistry. The gram-scale continuous-flow synthesis and efficient construction of bioactive molecules highlight its practical utility.