Fast,Efficient and Low E‐Factor One‐Pot Palladium‐Catalyzed Cross‐Coupling of (Hetero)Arenes

The homocoupling of aryl halides and the heterocoupling of aryl halides with either aryl bromides or arenes bearing an ortho‐lithiation directing group are presented. The use of a Pd catalyst, in combination with t‐BuLi, allows for the rapid and efficient formation of a wide range of polyaromatic compounds in a one pot procedure bypassing the need for the separate preformation of an organometallic coupling partner. These polyaromatic structures are obtained in high yields, in 10 min at room temperature, with minimal waste generation (E‐factors as low as 1.5) and without the need for strict inert conditions, making this process highly efficient and practical in comparison to classical methods. As illustration, several key intermediates of widely used BINOL‐derived structures are readily prepared.