Issue 5, 2019

Self-assembled M12L24 nanospheres as a reaction vessel to facilitate a dinuclear Cu(i) catalyzed cyclization reaction

Abstract

The application of large M12L24 nanospheres allows the pre-concentration of catalysts to reach high local concentrations, facilitating reactions that proceed through dinuclear mechanisms. The mechanism of the copper(I)-catalyzed cyclization of 4-pentynoic acid has been elucidated by means of a detailed mechanistic study. The kinetics of the reaction show a higher order in copper, indicating the formation of a bis-Cu intermediate as the key rate determining step of the reaction. This intermediate was further identified during catalysis by CIS-HRMS analysis of the reaction mixture. Based on the mechanistic findings, an M12L24 nanosphere was applied that can bind up to 12 copper catalysts by hydrogen bonding. This pre-organization of copper catalysts in the nanosphere results in a high local concentration of copper leading to higher reaction rates and turnover numbers as the dinuclear pathway is favored.

Graphical abstract: Self-assembled M12L24 nanospheres as a reaction vessel to facilitate a dinuclear Cu(i) catalyzed cyclization reaction

Supplementary files

Article information

Article type
Edge Article
Submitted
22 8 2018
Accepted
12 11 2018
First published
13 11 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2019,10, 1316-1321

Self-assembled M12L24 nanospheres as a reaction vessel to facilitate a dinuclear Cu(I) catalyzed cyclization reaction

S. Gonell, X. Caumes, N. Orth, I. Ivanović-Burmazović and Joost. N. H. Reek, Chem. Sci., 2019, 10, 1316 DOI: 10.1039/C8SC03767A

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