Issue 17, 2020

General and selective synthesis of primary amines using Ni-based homogeneous catalysts

Abstract

The development of base metal catalysts for industrially relevant amination and hydrogenation reactions by applying abundant and atom economical reagents continues to be important for the cost-effective and sustainable synthesis of amines which represent highly essential chemicals. In particular, the synthesis of primary amines is of central importance because these compounds serve as key precursors and central intermediates to produce value-added fine and bulk chemicals as well as pharmaceuticals, agrochemicals and materials. Here we report a Ni-triphos complex as the first Ni-based homogeneous catalyst for both reductive amination of carbonyl compounds with ammonia and hydrogenation of nitroarenes to prepare all kinds of primary amines. Remarkably, this Ni-complex enabled the synthesis of functionalized and structurally diverse benzylic, heterocyclic and aliphatic linear and branched primary amines as well as aromatic primary amines starting from inexpensive and easily accessible carbonyl compounds (aldehydes and ketones) and nitroarenes using ammonia and molecular hydrogen. This Ni-catalyzed reductive amination methodology has been applied for the amination of more complex pharmaceuticals and steroid derivatives. Detailed DFT computations have been performed for the Ni-triphos based reductive amination reaction, and they revealed that the overall reaction has an inner-sphere mechanism with H2 metathesis as the rate-determining step.

Graphical abstract: General and selective synthesis of primary amines using Ni-based homogeneous catalysts

Supplementary files

Article information

Article type
Edge Article
Submitted
23 Feb 2020
Accepted
25 Mar 2020
First published
25 Mar 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2020,11, 4332-4339

General and selective synthesis of primary amines using Ni-based homogeneous catalysts

K. Murugesan, Z. Wei, V. G. Chandrashekhar, H. Jiao, M. Beller and R. V. Jagadeesh, Chem. Sci., 2020, 11, 4332 DOI: 10.1039/D0SC01084G

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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