Radical [3+2] cycloaddition enables polysubstituted pyrrole synthesis <i>via</i> a visible-light-mediated reaction

We report a novel photocatalytic [3+2] annulation strategy employing <i>N</i>-aryl glycinates and 2-benzylidenemalononitrile partners for the efficient construction of polysubstituted pyrrole architectures. This methodology features operationally mild, redox-neutral conditions with exceptional functional group tolerance and broad substrate generality, while maintaining remarkable atom economy. Notably, the transformation utilizes dimethyl sulfoxide as both a reaction medium and a green oxidant. These features collectively offer a sustainable and practical approach to accessing poly-substituted pyrrole. The protocol has good scalability and excellent compatibility with biomolecules, which further underscores its potential utility.