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Heterobifunctional Rotaxanes for Asymmetric Catalysis
Author(s) -
Pairault Noël,
Zhu Hui,
Jansen Dennis,
Huber Alexander,
Daniliuc Constantin G.,
Grimme Stefan,
Niemeyer Jochen
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201913781
Subject(s) - catalysis , rotaxane , chemistry , amine gas treating , combinatorial chemistry , phosphoric acid , rational design , organocatalysis , catenane , nanotechnology , molecule , organic chemistry , enantioselective synthesis , materials science , supramolecular chemistry
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.