Noël Pairault1, Hui Zhu2, Dennis Jansen1, Alexander Huber1, Constantin G Daniliuc3, Stefan Grimme2, Jochen Niemeyer1. 1. Institute of Organic Chemistry and Center for Nanointegration Duisburg-Essen (CENIDE), University of Duisburg-Essen, Universitätsstrasse 7, 45141, Essen, Germany. 2. Mulliken Center for Theoretical Chemistry, Rheinische Friedrich-Wilhelms-Universität Bonn, Beringstrasse 4, 53115, Bonn, Germany. 3. Institute of Organic Chemistry, Corrensstr. 40, 48149, Münster, Germany.
Abstract
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.
Heterobifunctional class="Chemical">rotaxanes serve as efficieclass="Chemical">nt catalysts for the additioclass="Chemical">n of class="Chemical">n class="Chemical">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.
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