Palladium-catalyzed aerobic (1+2) annulation of Csp3-H bonds with olefin for the synthesis of 3-azabicyclo[3.1.0]hex-2-eneElectronic supplementary information (ESI) available. See DOI: 10.1039/c6cc09332a

A novel palladium-catalyzed aerobic (1+2) annulation was developed for the synthesis of 3-azabicyclo[3.1.0]hex-2-ene. The palladation of Csp 3 -H bonds took place twice at the same position in the whole reaction process. Preliminary mechanistic studies by in situ IR revealed that the second C-H palladation and reductive elimination might be slow steps. A novel Pd-catalyzed aerobic (1+2) annulation was developed and the palladation of Csp 3 -H bonds took place twice at the same position. Mechanistic studies by in situ IR revealed that the second C-H palladation and reductive elimination might be slow steps.