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  -