Heterobifunctional rotaxanes serve as efficient catalysts for the addition of malonates to Michael acceptors. We report a series of four different heterobifunctional rotaxanes, featuring an amine-based thread and a chiral 1,1'-binaphthyl-phosphoric-acid-based macrocycle. High-level DFT calculations provided mechanistic insights and enabled rational catalyst improvements, leading to interlocked catalysts that surpass their non-interlocked counterparts in terms of reaction rates and stereoselectivities.
Keywords: DFT; asymmetric catalysis; mechanically interlocked molecules; rotaxanes; supramolecular chemistry.
© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.