Enhancing the Catalytic Performance of Group I, II Metal Halides in the Cycloaddition of CO2 to Epoxides under Atmospheric Conditions by Cooperation with Homogeneous and Heterogeneous Highly Nucleophilic Aminopyridines: Experimental and Theoretical Study

Wuttichai Natongchai, Sergio Posada-Pérez, Chalida Phungpanya, Jesús Antonio Luque-Urrutia, Miquel Solà i Puig, Valerio D’Elia, Albert Poater i Teixidor

Research output: Contribution to journalArticleResearchpeer-review

Abstract

Compared to metal-organic complexes and transition-metal halides, group I metal halides are attractive catalysts for the crucial cycloaddition reaction of CO2 to epoxides as they are ubiquitously available and inexpensive, have a low molecular weight, and are not based on (potentially) endangered metals, especially for the case of sodium and potassium. Nevertheless, given their low intrinsic catalytic efficiency, they require the assistance of additional catalytic moieties. In this work, we show that by exploiting the high nucleophilicity of opportunely designed aminopyridines, catalytic systems based on alkaline metals can be formed, which allow the cycloaddition of CO2 to epoxides to proceed under atmospheric pressure at moderate temperatures. Importantly, the aminopyridine nucleophiles can be applied in their heterogenized form, leading to a recyclable catalytic system. An investigation of the reaction mechanism by density functional theory calculations shows that metal halide complexes and nucleophilic pyridines can work as a dual cooperative catalytic system where the use of aminopyridines leads to lower energy barriers for the opening of the epoxide ring, and halide-adducts are involved in the subsequent steps of CO2 insertion and ring closure.

Original languageAmerican English
Pages (from-to)2873-2886
Number of pages14
JournalThe Journal Of Organic Chemistry
Volume87
Issue number5
DOIs
Publication statusPublished - 4 Mar 2022

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