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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
ABI

Abstract

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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