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