Scott Sabrina S, Roşca Sorin-Claudiu, Gilmour Damon J, Brant Patrick, Schafer Laurel L
Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, British Columbia V6T 1Z1, Canada.
a2o Advanced Materials Inc., 2360 East Mall, Vancouver, British Columbia V6T 1Z1, Canada.
ACS Macro Lett. 2021 Oct 19;10(10):1266-1272. doi: 10.1021/acsmacrolett.1c00519. Epub 2021 Oct 4.
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 ,-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.
氢胺烷基化反应（HAA）被证明是一种很有前景的后聚合路线，可用于催化制备胺官能化的无规聚丙烯。使用最近报道的由一种α,α-螯合环状脲配体支撑的钽催化剂，乙烯基封端的聚丙烯（VTPP）被转化为芳基和烷基仲胺封端的聚烯烃。早期过渡金属催化的氢胺烷基化反应避免了仲胺合成通常所需的保护/脱保护步骤。该单步反应可以在多克规模下进行，溶剂用量最少，且原子经济性高，从而实现了优化的产物分离。通过多核核磁共振光谱、红外光谱、差示扫描量热法和热重分析法对材料进行了表征。通过安装荧光端基以及仲胺端基与羧酸部分缩合组装接枝共聚物，突出了反应性和未受保护的胺端基的实用性。
