Exploiting recognition-mediated assembly and reactivity in [2]rotaxane formation† †Electronic supplementary information (ESI) available: Details of kinetic experiments, computational methods and characterisation data for all compounds are provided. See DOI: 10.1039/c5sc04805b

• Published in: Chemical science (Cambridge) 2016-01, Vol.7 (4), p.2592-2603
• Main Authors: Vidonne, Annick, Kosikova, Tamara, Philp, Douglas
• Format: Article
• Language: English
• Subjects: Chemistry
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/c5sc04805b

A ternary complex facilitates the recognition-mediated formation of a [2]rotaxane. A small molecular reaction network exploits recognition-mediated reactive processes in order to drive the assembly and formation of both a self-replicating linear template (thread) and a [2]rotaxane, in which the linear template is encircled by a diamide macrocycle. Complementary recognition sites, placed at strategic positions on the reactive building blocks, drive these assembly and replication processes. Template-instructed experiments show that the thread is capable of efficient self-replication and that no cross-catalytic relationships exist between the thread and the [2]rotaxane. The rate of [2]rotaxane formation is insensitive to the addition of a preformed template, however, [2]rotaxane formation does show enhanced diastereoselectivity, most likely originating from its recognition-mediated formation through a ternary reactive complex.