Hydroaminoalkylation as a sustainable process to amine functionalized materials Sabrina S. Scott a , Laurel L. Schafera b a Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC, V6T 1Z1, Canada, b A2O Advanced Materials INC., 2360 East Mall, Vancouver, BC, V6T 1Z1, Canada Aminated materials are an underdeveloped class of functional polymers with hydrogen-bonding properties that result in interesting self-healing and adhesive properties. 1 The nucleophilicity, basicity, and polarity imparted by secondary amines allow for further synthetic elaboration or responsive material applications, making this class of materials highly desirable. Their troublesome syntheses result from undesirable amine catalyst inhibition in polymerization mechanisms, or uncontrolled radical reactivity, which results in unwanted chain scission. Methods have been developed using N-silane protecting groups on monomers, which reduces the atom economy; or feature tertiary amines which preclude further reactivity or hydrogen bonding capabilities. We have shown that post-polymerization hydroaminoalkylation is a promising, green, alternative to amine functionalized polymer synthesis. 2 This catalytic reaction is 100% atom economic, installing unprotected secondary amines onto alkene containing polymers. 3 Hydroaminoalkylation is a broadly applicable, able to couple a variety of aryl and alkyl amine substrates with alkene functionalized polyolefins in a single step and does not need directing or protecting groups.4 Further, hydroaminoalkylation is catalyzed by early transition metals, which are more abundant and less toxic than late transition metals, and the reactions can be performed in solvent-free conditions. This work overcomes current limitations in amine functionalized material synthesis,5 and is an inexpensive and easily accessible method to produce a new classes of amine containing polymers. In this presentation, current advances on tuning amine incorporation and accessible polymeric alkene substrates will be presented, along with implications of the amine functionality on material properties. References 1. Plummer, C. M.; Li, L.; Chen, Y. The Post-Modification of Polyolefins with Emerging Synthetic Methods. Polym. Chem. 2020, 11 (43), 6862–6872. 2. Scott, S. S.; Roşca, S.-C.; Gilmour, D. J.; Brant, P.; Schafer, L. L. Commodity Polymers to Functional Aminated Materials: Single-Step and Atom-Economic Synthesis by Hydroaminoalkylation. ACS Macro Lett. 2021, 10 (10), 1266–1272. 3. Edwards, P. M.; Schafer, L. L. Early Transition Metal-Catalyzed C–H Alkylation: Hydroaminoalkylation for Csp3–Csp3 Bond Formation in the Synthesis of Selectively Substituted Amines. Chem. Commun. 2018, 54 (89), 12543–12560. 4. DiPucchio, R. C.; Roşca, S.-C.; Schafer, L. L. Hydroaminoalkylation for the Catalytic Addition of Amines to Alkenes or Alkynes: Diverse Mechanisms Enable Diverse Substrate Scope. J. Am. Chem. Soc. 2022, 144 (26), 11459–11481. 5. Menendez Rodriguez, G.; Díaz-Requejo, M. M.; Pérez, P. J. Metal-Catalyzed Postpolymerization Strategies for Polar Group Incorporation into Polyolefins Containing C–C, C═C, and Aromatic Rings. Macromolecules 2021, 54 (11), 4971–4985.
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