Abstract
AbstractThe development of earth abundant 3d metal-based catalysts continues to be an important goal of chemical research. In particular, the design of base metal complexes for reductive amination to produce primary amines remains as challenging. Here, we report the combination of cobalt and linear-triphos (bis(2-diphenylphosphinoethyl)phenylphosphine) as the molecularly-defined non-noble metal catalyst for the synthesis of linear and branched benzylic, heterocyclic and aliphatic primary amines from carbonyl compounds, gaseous ammonia and hydrogen in good to excellent yields. Noteworthy, this cobalt catalyst exhibits high selectivity and as a result the -NH2 moiety is introduced in functionalized and structurally diverse molecules. An inner-sphere mechanism on the basis of the mono-cationic [triphos-CoH]+ complex as active catalyst is proposed and supported with density functional theory computation on the doublet state potential free energy surface and H2 metathesis is found as the rate-determining step.
Publisher
Springer Science and Business Media LLC
Subject
General Physics and Astronomy,General Biochemistry, Genetics and Molecular Biology,General Chemistry
Reference74 articles.
1. Beller, M. & Bolm, C. Transition Metals for Organic Synthesis (Wiley-VCH, NewYork, 2008).
2. Negishi, E.-i Magical power of transition metals: past, present, and future (Nobel lecture). Angew. Chem. Int. Ed. 50, 6738–6764 (2011).
3. Smith, G. V., Notheisz, F. Heterogeneous Catalysis in Organic Chemistry (Academic Press, San Diego, 1999).
4. Ertl, G., Knözinger, H., Weitkamp, J. Environmental Catalysis (WILEY‐VCH, 2008).
5. Drauz, K., Gröger, H., May, O. Enzyme Catalysis in Organic Synthesis (Wiley‐VCH, 2012).
Cited by
51 articles.
订阅此论文施引文献
订阅此论文施引文献,注册后可以免费订阅5篇论文的施引文献,订阅后可以查看论文全部施引文献