Enantioselective noncovalent synthesis of hydrogen-bonded double-rosette assemblies

L.J. Prins, Jeroen J. Verhage, J.J. Verhage, Feike de Jong, P. Timmerman, David Reinhoudt

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    Abstract

    The noncovalent synthesis of enantiomerically pure hydrogen-bonded assemblies (M)- and (P)-13(CA)6 is described. These dynamic assemblies are of one single handedness (M or P), but do not contain any chiral components. They are prepared by using the chiral memory concept: the induction of supramolecular chirality is achieved through initial assembly with chiral barbiturates, which are subsequently replaced by achiral cyanurates. This exchange process occurs quantitatively and without loss of the M or P handedness of the assemblies. Racemization studies have been used to determine an activation energy for racemization of 105.9±6.4 kJ mol-1 and a half-life time to racemization of 4.5 days in benzene at 18 °C. Kinetic studies have provided strong evidence that the rate-determining step in the racemization process is the dissociation of the first dimelamine component 1 from the assembly 13(CA)6. In addition to this, it was found that the expelled chiral barbiturate (RBAR or SBAR) acts as a catalyst in the racemization process. Blocking the dissociation process of dimelamines 1 from assembly 13(CA)6 by covalent capture through a ring-closing metathesis (RCM) reaction produces an increase of more than two orders of magnitude in the half-life time to racemization.
    Original languageUndefined
    Pages (from-to)2302-2313
    JournalChemistry: a European journal
    Volume8
    Issue number10
    DOIs
    Publication statusPublished - 2002

    Keywords

    • IR-37950
    • METIS-206209

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