Highly Efficient Ruthenium-Catalyzed N-Formylation of Amines with H₂ and CO₂

Lei Zhang; Zhaobin Han; Xiaoyu Zhao; Zheng Wang; Kuiling Ding

doi:10.1002/anie.201500939

Highly Efficient Ruthenium-Catalyzed N-Formylation of Amines with H₂ and CO₂

Angew Chem Int Ed Engl. 2015 May 18;54(21):6186-9. doi: 10.1002/anie.201500939. Epub 2015 Apr 7.

Authors

Lei Zhang¹, Zhaobin Han¹, Xiaoyu Zhao¹, Zheng Wang¹, Kuiling Ding²

Affiliations

¹ State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (P.R. China).
² State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (P.R. China). kding@mail.sioc.ac.cn.

PMID: 25850597
DOI: 10.1002/anie.201500939

Abstract

A highly efficient catalyst system based on ruthenium-pincer-type complexes has been discovered for N-formylation of various amines with CO2 and H2, thus affording the corresponding formamides with excellent productivity (turnover numbers of up to 1,940,000 in a single batch) and selectivity. Using a simple catalyst recycling protocol, the catalyst was reused for 12 runs in N,N-dimethylformamide production without significant loss of activity, thus demonstrating the potential for practical utilization of this cost-effective process. A one-pot two-step procedure for hydrogenation of CO2 to methanol via the intermediacy of formamide formation has also been developed.

Keywords: amines; hydrogenation; ligand effects; ruthenium; synthetic methods.