Acetoxypalladation of unactivated alkynes and capture with alkenes to give 1-acetoxy-1,3-dienes taking dioxygen as terminal oxidant.

A new and general protocol for the synthesis of 1-acetoxy-1,3-dienes by an acetoxypalladation/Heck cross-coupling/β-H elimination tandem process is described in which dioxygen is the terminal oxidant. Electron-rich and electron-deficient alkynes are both effective substrates in this system. It is the first example of acetoxypalladation of diarylalkynes.