1,3-N,O-Chelated early transition metal complexes show unique reactivity for the direct catalytic addition of amines to alkenes. Hydroaminoalkylation enables the addition of aryl- and alkylamines, as well as N-heterocycles, to add directly to terminal and internal unactivated alkenes to access diverse small molecule and materials products.¹ State-of-the-art catalysts feature N,O-chelating ureate ligands, with tuneable steric and electronic features and flexible bonding modes, to enable efficient C-H bond activation and Csp³-Csp³ bond formation. Hydroaminoalkylation addresses the fundamental thermodynamic challenge of hydroamination by making a C-C bond rather than a C-N bond. With this alternative disconnection, early transition metal catalyzed hydroaminoalkylation is a Green Chemistry approach for the synthesis of a range of selectively substituted amines. This 100% atom-economic reaction can be carried out on large scale using neat reaction conditions and could be transformative for the synthesis of nitrogen containing compounds in the pharmaceutical, agrochemical and functional materials industries. This regio- and diastereoselective catalytic technology offers a new disconnection for generating complex small molecule amines and N-heterocycles² or it can be used on large scale to access amine-containing, self-healing and adhesive materials with tuneable properties for application as underwater adhesives, anti-corrosion coatings and more.³

Figure 1. Ureate early-transition metal hydroaminoalkylation catalysts for the synthesis of small molecules and materials.

[1] DiPucchio, R. C.; Rosca, S.-C.; Schafer, L. L. Am. Chem. Soc. 2022, 144, 11459.

[2] Zheng, C. H. M., Balatsky, D. A., DiPucchio, R. C., Schafer, L. L. Org Lett. 2022, 6571.

[3] a) Gilmour, D. J.; Tomkovic, T.; Kuanr, N. ; Perry, M. R. ; Gildenast, H. ; Hatzikiriakos, S. G.;  Schafer, L. L. ACS Appl. Polym. Mater. 2021, 3, 2330. b) Scott, S. S.; Kaur, B.; Zheng, C. H. M; Brant, P.; Gilmour, D. J.; Schafer, L. L.   Am. Chem. Soc. 2023, 145, 22871.