Ethynylsulfone-Based Spontaneous Amino-yne Click Polymerization: A Facile Tool toward Regio- and Stereoregular Dynamic Polymers

Abstract

Development of efficient polymerizations is crucial for polymer science from which polymeric materials with versatile properties could be produced. In this work, a new and efficient spontaneous amino-yne click polymerization is successfully established by using activated diynes of bis(ethynylsulfone)s. Compared with the ester-activated diynes, that is, dipropiolates, bis(ethynylsulfone)s could polymerize with all kinds of diamines including aliphatic and aromatic primary and secondary ones under very mild reaction conditions, and soluble and thermally stable poly(β-aminovinylsulfone)s (PAVSs) with high weightaverage molecular weights (M w up to 160,000) and excellent regio-and stereoregularity (the ratio of E isomers up to 100%) were obtained in high yields (up to 99%). Due to the strong electron-withdrawing ability of sulfonyl groups, the resultant PAVSs show a dynamic property and could undergo the amine exchange, which makes the polymers readily degrade upon addition of monoamines. Moreover, this highly efficient spontaneous amino-yne click reaction could be used to facilely label and decorate proteins. Thus, this work not only establishes a more efficient amino-yne click polymerization, which could be used to label bioconjugates, but also provides a novel strategy to construct regio-and stereoregular dynamic polymers.

Aroylacetylene-Based Amino-Yne Click Polymerization toward Nitrogen-Containing Polymers

“…In the past decade, several novel amino-yne click polymerizations have been developed by our group. [22][23][24][25][26][27] Among our previous works, the spontaneous click polymerization of propiolates and amines reported in 2017 is most attractive, 25 since it can be conducted without extra heat or catalyst to prepare all regio-and stereospecific poly(β-aminoacrylate)s. This report brought a new perspective to researchers, and a series of exciting applications have been raised, especially in the field of biological applications. 28,29 However, there are still some shortcomings in this click polymerization to be overcome.…”

Catalyst‐Free Multicomponent Cyclopolymerizations of Diisocyanides, Activated Alkynes, and 1,4‐Dibromo‐2,3‐Butanedione: a Facile Strategy toward Functional Polyiminofurans Containing Bromomethyl Groups

“…[ 1 ] Multicomponent polymerization (MCP) has become a powerful tool for obtaining multifunctional advanced materials due to its excellent structural diversity, mild reaction conditions, and environmental benefits, and has thus attracted much attention. [ 2–11 ] In recent years, triple‐bond compounds, such as isonitriles [ 12–17 ] and alkynes, [ 18–24 ] have been widely used to prepare novel polymers through MCP. For instance, in 2018, Li et al.…”

Click chemistry strategies for the accelerated synthesis of functional macromolecules

“…Besides carbonyl groups, sulfones could also be used as a stronger activating group (B4) for all types of amines to afford high MW polymers up to 160 kDa, albeit with short monomer shelf life. 422 Notably, both poly(β-enaminone)s and poly(β-aminovinylsulfone)s resulting from amino-yne reaction exhibit dynamic properties. The newly formed bonds are easily cleaved by another small molecule primary amine assisted by Lewis acid, which makes the polymers readily degradable upon addition of amines.…”

“…This selectivity was attributed to intermolecular hydrogen‐bonding. Besides carbonyl groups, sulfones could also be used as a stronger activating group (B4) for all types of amines to afford high MW polymers up to 160 kDa, albeit with short monomer shelf life 422 . Notably, both poly(β‐enaminone)s and poly(β‐aminovinylsulfone)s resulting from amino‐yne reaction exhibit dynamic properties.…”