Kinetic Traps to Activate Stereomutation in Supramolecular Polymers

Jorge S Valera; Rafael Gómez; Luis Sánchez

doi:10.1002/anie.201809272

Kinetic Traps to Activate Stereomutation in Supramolecular Polymers

Angew Chem Int Ed Engl. 2019 Jan 8;58(2):510-514. doi: 10.1002/anie.201809272. Epub 2018 Dec 5.

Authors

Jorge S Valera¹, Rafael Gómez¹, Luis Sánchez¹

Affiliation

¹ Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Ciudad Universitaria s/n, 28040-, Madrid, Spain.

PMID: 30403830
DOI: 10.1002/anie.201809272

Abstract

The helical stereomutation in the kinetically controlled coassembly of the reported carbonyl-bridged triarylamines (CBTs) is described. The copolymerization of chiral CBTs (S)-1 or (R)-1 with achiral 2 in sergeants-and-soldiers (SaS) experiments results in a tunable helicity conditioned by the percentage of the chiral sergeant and by the cooling rate. The dissimilar inherent chirality of the extended monomeric (M) and intramolecularly H-bonded metastable (M*) species, as well as the different stability of the kinetic trap of the chiral CBTs (S)-1/(R)-1 and the achiral CBT 2, condition the chirality transfer and afford J-aggregates of inverse handedness.

Keywords: chirality; out-of-equilibrium; stereomutation; tunable helicity.