The development of transition metal complexes capable of stabilizing high-energy intermediates is central to advancing selective group-transfer reactions. Traditional gold nitrene transfer involves subtrate activation and formation of α-imino gold carbenes as key intermediates, with discrete gold-nitrene species remaining elusive.^[1-3]

Here, we report a structurally characterized Au(III) complex supported by a tridentate (N^C^C) ligand and bearing an azido moiety, which serves as a direct precursor to a gold-bound nitrene. Upon photochemical activation,^[4-6] the azide undergoes dinitrogen extrusion to generate a reactive Au(III)-nitrene species that engages in C-H insertion into aldehydes, yielding isolable Au(III)-amido intermediates. These complexes represent the first examples of direct nitrene transfer to aldehydes with gold(III). Furthermore, catalytic amidation is achieved under mild conditions, with mechanistic and kinetic studies providing strong support for the proposed pathway. Beyond C-H amidation, the azido complex facilitates nitrene transfer to phosphines and displays additional reactivity, including C-H metalation and click reactions, highlighting its modular and substrate-dependent versatility.

[1] L.-W. Ye, X.-Q. Zhu, R. L. Sahani, Y. Xu, P.-C. Qian, R.-S. Liu, Chemical Reviews, 2020, 121, 9039–9112.

[2] E. Aguilar, J. Santamaría, Organic Chemistry Frontiers, 2019, 6, 1513–1540.

[3] P. W. Davies, M. Garzón, Asian Journal of Organic Chemistry, 2015, 4, 694–708. 

[4] J. Mieres-Pérez, E. Mendez-Vega, K. Velappan, W. Sander, The Journal of Organic Chemistry, 2015, 80, 11926–11931.

[5] J. Sun, J. Abbenseth, H. Verplancke, M. Diefenbach, B. de Bruin, D. Hunger, C. Würtele, J. van Slageren, M. C. Holthausen, S. Schneider, Nature Chemistry, 2020, 12, 1054–1059.

[6] M. Janssen, T. Frederichs, M. Olaru, E. Lork, E. Hupf, J. Beckmann, Science, 2024, 385, 318–321.