Ambient-pressure alkoxycarbonylation for sustainable synthesis of ester

Bin Zhang; Haiyang Yuan; Ye Liu; Zijie Deng; Mark Douthwaite; Nicholas F Dummer; Richard J Lewis; Xingwu Liu; Sen Luan; Minghua Dong; Tianjiao Wang; Qingling Xu; Zhijuan Zhao; Huizhen Liu; Buxing Han; Graham J Hutchings

doi:10.1038/s41467-024-52163-2

Ambient-pressure alkoxycarbonylation for sustainable synthesis of ester

Nat Commun. 2024 Sep 7;15(1):7837. doi: 10.1038/s41467-024-52163-2.

Authors

Bin Zhang^#^{1

2}, Haiyang Yuan^#³, Ye Liu^#^{1

4}, Zijie Deng^{1

5}, Mark Douthwaite⁶, Nicholas F Dummer², Richard J Lewis², Xingwu Liu⁷, Sen Luan^{1

5}, Minghua Dong^{1

5}, Tianjiao Wang^{1

5}, Qingling Xu⁸, Zhijuan Zhao⁹, Huizhen Liu^{10

11}, Buxing Han^{1

5}, Graham J Hutchings²

Affiliations

¹ Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, Center for Carbon Neutral Chemistry, Institute of Chemistry, Chinese Academy of Sciences, 100190, Beijing, China.
² Max Planck-Cardiff Centre on the Fundamentals of Heterogeneous Catalysis FUNCAT, Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Cardiff, CF24 4HQ, UK.
³ Key Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and Technology, 130 Meilong Road, 200237, Shanghai, China.
⁴ Laboratory of Living Materials at the State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, 430070, Wuhan, Hubei, China.
⁵ School of Chemical Sciences, University of Chinese Academy of Sciences, 101408, Beijing, China.
⁶ Max Planck-Cardiff Centre on the Fundamentals of Heterogeneous Catalysis FUNCAT, Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Cardiff, CF24 4HQ, UK. [email protected].
⁷ National Energy Center for Coal to Liquids, Synfuels China Co., Ltd, Huairou District, 101400, Beijing, China.
⁸ School of Chemical Sciences, University of Chinese Academy of Sciences, 101408, Beijing, China. [email protected].
⁹ Institute of Chemistry, Chinese Academy of Sciences, 100190, Beijing, China.
¹⁰ Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, Center for Carbon Neutral Chemistry, Institute of Chemistry, Chinese Academy of Sciences, 100190, Beijing, China. [email protected].
¹¹ School of Chemical Sciences, University of Chinese Academy of Sciences, 101408, Beijing, China. [email protected].

^# Contributed equally.

Abstract

Alkoxycarbonylation reactions are common in the chemical industry, yet process sustainability is limited by the inefficient utilization of CO. In this study, we address this issue and demonstrate that significant improvements can be achieved by adopting a heterogeneously catalyzed process, using a Ru/NbO_x catalyst. The Ru/NbO_x catalyst enables the direct synthesis of methyl propionate, a key industrial commodity, with over 98% selectivity from CO, ethylene and methanol, without any ligands or acid/base promoters. Under ambient CO pressure, a high CO utilization efficiency (336 mmol_estermol_CO^-1h^-1) is achieved. Mechanistic investigations reveal that CO undergoes a methoxycarbonyl (COOCH₃) intermediate pathway, attacking the terminal carbon atom of alkene and yielding linear esters. The origins of prevailing linear regioselectivity in esters are revealed. The infrared spectroscopic feature of the key COOCH₃ species is observed at 1750 cm^-1 (C=O vibration) both experimentally and computationally. The broad substrate applicability of Ru/NbO_x catalyst for ester production is demonstrated. This process offers a sustainable and efficient approach with high CO utilization and atom economy for the synthesis of esters.