Spontaneous Amino-yne Click Polymerization: A Powerful Tool toward Regio- and Stereospecific Poly(β-aminoacrylate)s

Abstract

Efficient synthesis of poly(enamine)s has been a great challenge because of their poor stability, poor solubility, and low molecular weights. In this work, a spontaneous amino-yne click polymerization for the efficient preparation of poly(enamine)s was established, which could proceed with 100% atom efficiency under very mild conditions without any external catalyst. Through systematic optimization of the reaction conditions, several soluble and thermally stable poly(β-aminoacrylate)s with high molecular weights (M up to 64400) and well-defined structures were obtained in excellent yields (up to 99%). Moreover, the polymerization can perform in a regio- and stereospecific fashion. Nuclear magnetic resonance spectra analysis revealed that solely anti-Markovnikov additive products with 100% E-isomer were obtained. The reaction mechanism was well demonstrated with the assistance of density functional theory calculations. In addition, by introducing the tetraphenylethene moiety, the resulting polymers exhibit unique aggregation-induced emission characteristics and could be applied in explosives detection and bioimaging. This polyhydroamination is a new type of click polymerization and opens up enormous opportunities for preparing functional polymeric materials.

Fast surface immobilization of native proteins through catalyst-free amino-yne click bioconjugation

“…S1, ESI †), indicative of the successful reaction of APTES with diyne 1. 30 This result suggests that the ethynyl groups of 1 can react with amino groups of APTES on the surface effectively.…”

“…In our previous work, we have developed a spontaneous amino-yne click polymerization that enjoys the advantages of atom economy, mild reaction and catalyst-free conditions, and stereo-and regioselectivity, etc. [28][29][30][31][32] More recently, the aminoyne click reaction was proved to hold great potential for bioconjugation applications. 33,34 Attracted by this highly efficient spontaneous amino-yne click reaction, herein, we applied it in functionalizing surfaces and sequentially immobilizing native bioconjugates for the rst time.…”

Ti‐Catalyzed Hydroamination for the Synthesis of Amine‐Containing π‐Conjugated Materials

“…Compounds 2-6 were synthesized using the same conditions, and could easily be isolateda sp ure compoundsb yf iltration, as the products precipitate from the reactionsolution. Conversely,a ne lectron-poor central ring (5)o re lectron-richs ide rings (4)r esult in increased quantum yields. Identical reaction conditions were used in each case and no significant changes in reactivity or selectivity could be observed.…”

Progress on Catalytic Systems Used in Click Polymerization

“…Besides the spontaneous thiol‐yne click polymerization, we also succeeded in established spontaneous amino‐yne click polymerization, which processes in a regiospecific and stereospecific fashion under very mild conditions as well . As displayed in Scheme , the polymerization of propiolates and amines 190–193 in dichloromethane at room temperature readily generated thermally stable poly(β‐aminoacrylates) 194–201 with high molecular weights ( M w up to 64 400) and well‐defined structures in excellent yields (up to 99%) after 3 h. In addition, by incorporating the TPE moiety, the yielded polymers show the unique AIE features, and could be used as fluorescent probes to detect explosives and specifically label lysosomes.…”