Accessing secondary amine containing fine chemicals and polymers with an earth-abundant hydroaminoalkylation catalyst

Titanium-catalyzed hydroaminoalkylation has emerged as an atom-economical, earth-abundant synthesis of N-containing products. Secondary amines are added to diverse alkenes with branched regioselectivity by a catalytic system that is assembled in one step using Ti(NMe2)(4) and urea ligand. Both 1,1- and 1,2-disubstituted alkenes are aminated with this titanium catalyst. Sterically enhanced aryl and alkyl amines are installed onto silylether functionalized alkenes to synthesize precursors for biologically active substrates. Regioselective formation of branched amine functionalized materials are prepared from vinyl terminated polypropylene to access aminated materials. Such materials are potentially useful adhesives, compatibilizers, and reactive macromolecules to fabricate functional materials. A life cycle analysis of competing tantalum and titanium catalysts is provided to quantify the environmental impacts and demonstrate how titanium-catalyzed hydroaminoalkylation is a greener solution to amine terminated polypropylene synthesis.

Automated summary

Titanium-catalyzed hydroaminoalkylation is a versatile method for synthesizing N-containing products with high atom efficiency and using abundant resources. This catalytic system, assembled in one step using Ti(NMe2)(4) and urea ligand, enables regioselective addition of secondary amines to diverse alkenes. The titanium catalyst can aminate both 1,1- and 1,2-disubstituted alkenes, allowing for the synthesis of precursors for biologically active substances. Additionally, the application of this method in the synthesis of functional materials, such as adhesives and compatibilizers, is explored.