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Twofold C-H annulation of readily available formamides and alkynes without built-in chelating groups was achieved, providing a series of chiral ferrocenes in 40-98% yield and 93-99% ee. Bulky chiral SPO ligand-enabled Ni-Al bimetallic catalysis proved to be critical to high reactivity and high selectivity. © 2020 WILEY-VCH Verlag GmbH Co. KGaA, Weinheim.A new methodology for the double N-arylation of diketopyrrolopyrroles with aryl triflates has been developed. It is now possible to prepare diketopyrrolopyrroles bearing N-substituents der