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Prospects and challenges for nitrogen-atom transfer catalysis

Nature Reviews Chemistry volume 7, pages 424–438 (2023)Cite this article

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Abstract

Conversion of C–H bonds to C–N bonds via C–H amination promises to streamline the synthesis of nitrogen-containing compounds. Nitrogen-group transfer (NGT) from metal nitrenes ([M]–NR complexes) has been the focus of intense research and development. By contrast, potentially complementary nitrogen-atom transfer (NAT) chemistry, in which a terminal metal nitride (an [M]–N complex) engages with a C–H bond, is underdeveloped. Although the earliest examples of stoichiometric NAT chemistry were reported 25 years ago, catalytic protocols are only now beginning to emerge. Here, we summarize the current state of the art in NAT chemistry and discuss opportunities and challenges for its development. We highlight the synthetic complementarity of NGT and NAT and discuss critical aspects of nitride electronic structure that dictate the philicity of the metal-supported nitrogen atom. We also examine the characteristic reactivity of metal nitrides and present emerging strategies and remaining obstacles to harnessing NAT for selective, catalytic nitrogenation of unfunctionalized organic small molecules.

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Fig. 1: NGT versus NAT.
Fig. 2: Electronic structure and reactivity of metal nitrides.
Fig. 3: Nucleophilic nitrides.
Fig. 4: Aziridination reactions.
Fig. 5: Electrophilic nitrides.
Fig. 6: Ambiphilic and radical nitrides.
Fig. 7: Cycloaddition reactions from metal nitrides.
Fig. 8: Oxidative cleavage by metal nitrides.

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Acknowledgements

The authors gratefully acknowledge the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Catalysis Program (DE-SC0018977), the Welch Foundation (A-1907) and the National Science Foundation (CAREER 1848135) Alliances for Graduate Education and the Professoriate Fellowship to M.N.C.

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    Mario N. Cosio & David C. Powers

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All authors contributed equally to the preparation of this manuscript.

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Glossary

Metallonitrene

A recently introduced term, also called a metal nitrenido. A possible electronic formulation of the [M]–N fragment in which two electron holes are localized on the nitrogen atom.

Metal nitrene

An [M]–NR fragment.

Metal nitrides

An [M]–N fragment.

Nitrogen-atom transfer

(NAT). A reaction in which the substrate is engaged by a metal nitride.

Nitrogen-group transfer

(NGT). A reaction in which the substrate is engaged by a metal nitrenoid.

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Cosio, M.N., Powers, D.C. Prospects and challenges for nitrogen-atom transfer catalysis. Nat Rev Chem 7, 424–438 (2023). https://doi.org/10.1038/s41570-023-00482-1

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