Impact Factor:7.7

DOI number:10.1002/cssc.202500949

Journal:CHEMSUSCHEM

Abstract:Direct carbonylation of the C(sp3)Cl bond remains a challenging transformation in the chemical industry. The usual use of precious metals, the high cost of ligands, and the lack of recyclability of catalysts make their industrial application on a large scale impossible. A ligand-free cobalt-based catalyst for the alkoxycarbonylation of chloroacetates to dialkyl malonates, which are important industrial intermediates, is reported here. This catalyst uses an extremely inexpensive precursor, CoCO3, with a very low catalyst loading (0.5 mol%) to achieve product yields of up to 99% with nearly 100% chemoselectivity. Solvents and previously essential phase transfer agents are not needed. Most importantly, the catalyst can be easily recycled without losing its activity and selectivity. Over 95% product yield is achieved even after 8 recycles. The feasibility of this system is demonstrated through 14 examples of the alkoxycarbonylation reaction. Fourier transform infrared spectroscopy investigations identified the active cobalt species as [Co(CO)4]−. As the first recyclable cobalt-based catalyst, this ligand-free system has great potential for large-scale industrial transfer.

Co-author:Wenyu Wang, Zhusong Cao, Yuya Hu, Rui Sang,* Qingshan Kong, Qicai Xue, and Baoxin Zhang*

Indexed by:Journal paper

Correspondence Author:Rui Sang；Baoxin Zhang

Document Type:J

Volume:18

Issue:17

Translation or Not:no

Date of Publication:2025-09-01

Included Journals:SCI

Links to published journals:http://doi.org/10.1002/cssc.202500949