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1.2.3.1.2 Nickel Catalysis

DOI: 10.1055/sos-SD-223-00066

Martin, A. R.Science of Synthesis: N-Heterocyclic Carbenes in Catalytic Organic Synthesis, (20161170.

Pioneered by Fort, the first use of an in situ generated nickel/NHC catalyst was reported in 2001[‌34‌] on simple substrates and later extended to a wider range of amines and anilines, including an intramolecular amination process.[‌35‌‌37‌] This general methodology relies on the use of a nickel(II) precursor and an NHC salt in combination with sodium hydride to generate the nickel(0) active species. The need for a strong base hampers reactions in the presence of sensitive functional groups on both the amine and aryl chloride. This limitation is a common feature in nickel-catalyzed aryl amination. Nevertheless, among other examples is the efficient coupling of chlorobenzene with an amine bearing a dimethyl acetal moiety to give 2,2-dimethoxy-N-methyl-N-phenylethanamine (28) (Scheme 12).[‌34‌]

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