eprintid: 10189560 rev_number: 7 eprint_status: archive userid: 699 dir: disk0/10/18/95/60 datestamp: 2024-03-22 16:56:29 lastmod: 2024-03-22 16:56:29 status_changed: 2024-03-22 16:56:29 type: article metadata_visibility: show sword_depositor: 699 creators_name: Yeung, Angus creators_name: Zwijnenburg, Martijn A creators_name: Orton, Georgia RF creators_name: Robertson, Jennifer H creators_name: Barendt, Timothy A title: Investigating the diastereoselective synthesis of a macrocycle under Curtin–Hammett control ispublished: inpress divisions: UCL divisions: B04 divisions: C06 divisions: F56 note: This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. abstract: 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. date: 2024-03-05 date_type: published publisher: Royal Society of Chemistry (RSC) official_url: https://doi.org/10.1039/D3SC05715A oa_status: green full_text_type: pub language: eng primo: open primo_central: open_green verified: verified_manual elements_id: 2261544 doi: 10.1039/d3sc05715a lyricists_name: Zwijnenburg, Martinus Antonius lyricists_id: MAZWI52 actors_name: Zwijnenburg, Martinus Antonius actors_id: MAZWI52 actors_role: owner full_text_status: public publication: Chemical Science issn: 2041-6520 citation: Yeung, Angus; Zwijnenburg, Martijn A; Orton, Georgia RF; Robertson, Jennifer H; Barendt, Timothy A; (2024) Investigating the diastereoselective synthesis of a macrocycle under Curtin–Hammett control. Chemical Science 10.1039/d3sc05715a <https://doi.org/10.1039/d3sc05715a>. (In press). Green open access document_url: https://discovery.ucl.ac.uk/id/eprint/10189560/1/d3sc05715a.pdf