Abstract: | This work reports the first success of the nitroso‐Povarov reaction, involving gold‐catalyzed [4+2] annulations of nitrsoarenes with substituted cyclopentadienes. In this catalytic sequence, nitrosoarenes presumably attack gold‐π‐dienes by a 1,4‐addition pathway, generating allylgold nitrosonium intermediates to complete an intramolecular cyclization. Acyclic dienes are also applicable substrates, and affording oxidative nitroso‐Povarov products. |