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Four chiral phosphapalladacycle complexes functionalized with the malonate moiety at the chiral carbon have been synthesized via a consecutive asymmetric hydrophosphination and cyclometallation protocol. High conversions were achieved in the P–H addition reaction, which was itself catalyzed by a phosphapalladacycle. Moderate to good enantioselectivities, were obtained for this step depending on the nature of the functional groups present on the naphthalene backbone. In contrast, the outcome of the subsequent cyclometallation reaction relies highly on the character of the functional groups. The catalytic potential of the synthesized phosphapalladacycle complexes was evaluated in the hydrophosphination reaction of chalcone with moderate results. Four new chiral phosphapalladacycles with designed stereo‐ and electronic properties were prepared by catalysis and by optical resolution and comprehensively characterised. The impact of incorporation of malonate moiety at the chiral carbon and modification of the naphthalene system was studied for the asymmetric hydrophosphination of chalcone. [ABSTRACT FROM AUTHOR]