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Asymmetric Catalysis with a Mechanically Point-Chiral Rotaxane

Yusuf ÇakmakSchool of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, United KingdomSündüs Erbaş-ÇakmakSchool of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, United KingdomDavid A. LeighSchool of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, United Kingdom
2016en
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Mechanical point-chirality in a [2]rotaxane is utilized for asymmetric catalysis. Stable enantiomers of the rotaxane result from a bulky group in the middle of the thread preventing a benzylic amide macrocycle shuttling between different sides of a prochiral center, creating point chirality in the vicinity of a secondary amine group. The resulting mechanochirogenesis delivers enantioselective organocatalysis via both enamine (up to 71:29 er) and iminium (up to 68:32 er) activation modes.

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