%0 Journal Article
%@ 2041-6520
%A Yeung, Angus
%A Zwijnenburg, Martijn A
%A Orton, Georgia RF
%A Robertson, Jennifer H
%A Barendt, Timothy A
%D 2024
%F discovery:10189560
%I Royal Society of Chemistry (RSC)
%J Chemical Science
%T Investigating the diastereoselective synthesis of a macrocycle under Curtin–Hammett control
%U https://discovery.ucl.ac.uk/id/eprint/10189560/
%X This work sheds new light on the stereoselective synthesis of chiral macrocycles containing twisted aromatic units, valuable π-conjugated materials for recognition, sensing, and optoelectronics. For the first time, we use the Curtin–Hammett principle to investigate a chiral macrocyclisation reaction, revealing the potential for supramolecular π–π interactions to direct the outcome of a dynamic kinetic resolution, favouring the opposite macrocyclic product to that expected under reversible, thermodynamically controlled conditions. Specifically, a dynamic, racemic perylene diimide dye (1 : 1 P : M) is strapped with an enantiopure (S)-1,1′-bi-2-naphthol group (P-BINOL) to form two diastereomeric macrocyclic products, the homochiral macrocycle (PP) and the heterochiral species (PM). We find there is notable selectivity for the PM macrocycle (dr = 4 : 1), which is rationalised by kinetic templation from intramolecular aromatic non-covalent interactions between the P-BINOL π-donor and the M-PDI π-acceptor during the macrocyclisation reaction.
%Z This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.