TY - INPR N1 - This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. JF - Chemical Science A1 - Yeung, Angus A1 - Zwijnenburg, Martijn A A1 - Orton, Georgia RF A1 - Robertson, Jennifer H A1 - Barendt, Timothy A PB - Royal Society of Chemistry (RSC) TI - Investigating the diastereoselective synthesis of a macrocycle under Curtin?Hammett control SN - 2041-6520 Y1 - 2024/03/05/ AV - public N2 - This work sheds new light on the stereoselective synthesis of chiral macrocycles containing twisted aromatic units, valuable ?-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 ??? 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 ?-donor and the M-PDI ?-acceptor during the macrocyclisation reaction. UR - https://doi.org/10.1039/D3SC05715A ID - discovery10189560 ER -