Self-assembled M12L24nanospheres as a reaction vessel to facilitate a dinuclear Cu(i) catalyzed cyclization reaction

Gonell S, Caumes X, Orth N, Ivanovic-Burmazovic I, Reek JNH (2019)

Publication Type: Journal article

Publication year: 2019

Journal

Chemical Science Royal Society of Chemistry

Book Volume: 10

Pages Range: 1316-1321

Journal Issue: 5

DOI: 10.1039/c8sc03767a

Abstract

The application of large M 12 L 24 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 M 12 L 24 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.

Authors with CRIS profile

Nicole Orth Lehrstuhl für Bioanorganische Chemie Ivana Ivanovic-Burmazovic Lehrstuhl für Bioanorganische Chemie

Involved external institutions

University of Amsterdam NL Netherlands (NL)

How to cite

APA:

Gonell, S., Caumes, X., Orth, N., Ivanovic-Burmazovic, I., & Reek, J.N.H. (2019). Self-assembled M12L24nanospheres as a reaction vessel to facilitate a dinuclear Cu(i) catalyzed cyclization reaction. Chemical Science, 10(5), 1316-1321. https://dx.doi.org/10.1039/c8sc03767a

MLA:

Gonell, Sergio, et al. "Self-assembled M12L24nanospheres as a reaction vessel to facilitate a dinuclear Cu(i) catalyzed cyclization reaction." Chemical Science 10.5 (2019): 1316-1321.

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