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Abstract

Amine-containing materials are a highly desired class of compounds due to their interesting physical properties. Amine functionalized materials have an increased compatibility with polar substrates compared to nonpolar olefin materials and have been applied to various applications. Current amine containing materials are often based on the commercially available library of amine monomers which offer access to only a limited range of materials able to be used industrially. Expanding the library of amine monomers is essential for increasing the diversity of amine containing materials for use in diverse applications. As well, by expanding the scope of amine monomers new applications for amine materials may be realized. The synthesis of amine materials remains nontrivial and is often plagued by laborious, multi-step synthetic routes, leading to low overall yields. Herein, a synthetic protocol utilizing hydroaminoalkylation to catalytically assemble amine monomers on multigram scale with 100% atom economy is reported. Selective mono-hydroaminoalkylation of dienes using Ti- or Ta- based catalysts has resulted in a library of aminoolefins with long methylene spacers and both aryl and alkyl functionalities have been incorporated on the amine. The resultant aminoolefins are further N-alkylated to synthesize tertiary aminoolefins. Taking advantage of the remaining pendent olefin in the monomer, homo- and co-polymerizations were attempted to produce amine-enchained materials via coordination-insertion polymerization strategies. In addition to the aminoolefin polymers which could be targeted with the monoaminated dienes, diamines could be synthesized which could provide an alternate route to amine-containing polymers. Diamines were synthesized by selectively diaminating dienes via hydroaminoalkylation. Using this strategy, diamines with varying electronic and steric parameters were synthesized. The diamines could be used in various polymerization strategies to develop polyureas, or polyamides. By selectively monoaminating or diaminating dienes using hydroaminoalkylation, a library of amine monomers were synthesized and tested in polymerization. This two-step protocol lays the groundwork to generate materials with tunable electronic and steric parameters by allowing flexibility to alter either the substituents around the amine or the length of the diene. This catalytic, atom economic, green approach provides an opportunity for a new class of amine materials to address challenges in materials chemistry.