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

Abstract

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.