Hydroaminoalkylation (HAA) is demonstrated to be a promising postpolymerization route to catalytically prepare amine-functionalized atactic polypropylene. Using a recently reported tantalum catalyst supported by a N,O-chelating cyclic ureate ligand, vinyl-terminated polypropylene (VTPP) is transformed into both aryl and alkyl secondary amine-terminated polyolefins. Early transition-metal-catalyzed hydroaminoalkylation avoids protection/deprotection protocols typically required for secondary amine synthesis. This single-step reaction can be performed at multigram scale with minimal solvent and is atom economic, thereby allowing for optimized product isolation. Materials are characterized by multinuclear NMR spectroscopy, IR spectroscopy, DSC, and TGA. The utility of the reactive and unprotected amine terminus is highlighted by the installation of a fluorescent end group and the assembly of a graft copolymer by condensation of the secondary amine terminus with carboxylic acid moieties.

Titanium-catalyzed hydroaminoalkylation has emerged as an atom-economical, earth-abundant synthesis of N-containing products.

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