Homogeneous cobalt-catalyzed reductive amination for synthesis of functionalized primary amines

Kathiravan Murugesan, Zhihong Wei, Vishwas G. Chandrashekhar, Helfried Neumann, Anke Spannenberg, Haijun Jiao, Matthias Beller, Rajenahally V. Jagadeesh

Research output: Contribution to journalArticlepeer-review

56 Scopus citations

Abstract

The 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.

Original languageEnglish
Article number5443
JournalNature Communications
Volume10
Issue number1
DOIs
StatePublished - 1 Dec 2019
Externally publishedYes

Fingerprint

Dive into the research topics of 'Homogeneous cobalt-catalyzed reductive amination for synthesis of functionalized primary amines'. Together they form a unique fingerprint.

Cite this