Palladium-metalated PCN-222 enables the aerobic photo-oxidative cross-condensation of anilines with benzylic amines yielding a series of linear and cyclic imines. The reaction is very efficient under mild conditions, which allows the isolation of simple, yet elusive, intermediates such as 2-(benzylideneamino)­aniline and 2-(benzylideneamino)­phenols. Recyclability studies show excellent activity and selectivity after five runs. The methodology was successfully applied for the synthesis of an antitumor agent (PMX-610).

A novel iron‐catalyzed borylation of propargylic acetates leading to allenylboronates has been developed. The method allows the preparation of a variety of di‐, tri‐ and tetrasubstituted allenylboronates at room temperature with good functional group compatibility. Stereochemical studies show that an anti‐SN2’ displacement of acetate by boron occurs; this also allows transfer of chirality to yield enantiomerically enriched allenylboronates. The synthetic utility of this protocol was further substantiated by transformations of the obtained allenylboronates including oxidation and propargylation.