Thiolative Annulation of N-Benzyl-N-cyanopropiolamides Leading to Divergent Synthesis of Pyrroloquinazolin-1-ones and Maleimides

An unprecedented successive radical-promoted thiolative annulation/Pd-catalyzed C-H amination of N-benzyl-N-cyanopropiolamides to access pyrrolo[2,1-b]quinazolin-1(9H)-ones in a one-pot manner is described. Moreover, altering the amination step with oxidation (reagent switch) offered maleimides from the same set of readily accessible precursors. Both transformations display versatility across a wide range of substrates, enabling the efficient access to various functionalized quinazolin-1-ones and maleimides in good yields.