Self-assembled M12 L24 nanospheres as a reaction vessel to facilitate a dinuclear Cu(i) catalyzed cyclization reaction

Chemical Science
Sergio GonellJoost N H Reek

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.

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Citations

Dec 10, 2019·Chemistry : a European Journal·Christopher G P TaylorMichael D Ward
Jan 28, 2021·Chemical Society Reviews·Jonathan Trouvé, Rafael Gramage-Doria
May 20, 2021·Chemical Society Reviews·Giorgio OlivoStefano Di Stefano
Jun 8, 2021·Chemical Science·David A PooleJoost N H Reek
Jun 26, 2021·Chemical Science·Eduard O BobylevJoost N H Reek
Jun 23, 2021·Chemistry : a European Journal·Eduard O BobylevJoost N H Reek
Jul 31, 2021·Inorganic Chemistry·Eduard O BobylevJoost N H Reek
Aug 30, 2019·Journal of the American Chemical Society·Kaj M van VlietBas de Bruin
Dec 23, 2021·Organic & Biomolecular Chemistry·Arnout P T HartendorpJan H van Maarseveen

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Methods Mentioned

BETA
NMR

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