@article{discovery10189560, publisher = {Royal Society of Chemistry (RSC)}, month = {March}, year = {2024}, title = {Investigating the diastereoselective synthesis of a macrocycle under Curtin-Hammett control}, journal = {Chemical Science}, note = {This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.}, issn = {2041-6520}, abstract = {This work sheds new light on the stereoselective synthesis of chiral macrocycles containing twisted aromatic units, valuable {\ensuremath{\pi}}-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 {\ensuremath{\pi}}-{\ensuremath{\pi}} 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 {\ensuremath{\pi}}-donor and the M-PDI {\ensuremath{\pi}}-acceptor during the macrocyclisation reaction.}, url = {https://doi.org/10.1039/D3SC05715A}, author = {Yeung, Angus and Zwijnenburg, Martijn A and Orton, Georgia RF and Robertson, Jennifer H and Barendt, Timothy A} }