X‐yne click polymerization

Abstract

Alkyne‐based click polymerizations have been nurtured into a powerful synthetic technique for the preparation of new polymers with advanced structures and versatile properties. Among them, the emerging thiol‐yne, hydroxyl‐yne, and amino‐yne click polymerizations have made remarkable progress from reactions to applications. These polymerizations avoid the usage of inherently dangerous monomers and are safer to operate than the classical azide‐alkyne click polymerization (AACP), making them more prospective for diverse applications. To greatly promote the new alkyne‐based click polymerizations beyond AACP, a new concept of “X‐yne click polymerization” is proposed to unify them, where “X” denotes the monomers that can react with alkynes under mild reaction conditions, including thiols, alcohols, amines, and other promising ones. In this review, we mainly present a brief account of the progress of X‐yne click polymerization and discuss in detail the challenges and opportunities in this field.

Synthesis of differentiated sulfur-containing polymers by regiodivergent polymerization of Morita–Baylis–Hillman acetates and thiols

“…of TEA at 25 °C. 9 Gratifyingly, the polymer α-P1a/2a was successfully obtained with excellent α-regioselectivity (>99 : 1 rr), resulting in a number-average molecular weight ( M n ) of 6.4 kDa and a molecular weight dispersity ( Đ ) of 1.75 (Table 1, entry 1). In comparison, the polymerization proceeded slowly in the absence of TEA, indicating that the organic base was important in promoting polymerization (Table 1, entry 2).…”

Ethynyl-Directed Dual C(sp3)–H Activation Polymerization to Construct Regio- and Stereoregular C(sp3)–C(sp3) Bond Polymers

“…From the Φ F results, PABs contained TPE moieties possessing aggregation-enhanced emission (AEE) or AIE features. − Thus, their emission behaviors were systematically studied in DMF/H 2 O mixed solvents with different water fractions ( f w ). P 1b2a is taken as an example, as illustrated in Figure D.…”

Click-Reaction-Mediated Chemotherapy and Photothermal Therapy Synergistically Inhibit Breast Cancer in Mice

“…Meanwhile, highly efficient reactions under mild reaction conditions present significant promise for biomedical applications. Diverse reactions, including Staudinger ligation, , quadricylane ligation, Diels–Alder reaction, − strain promoted azide–alkyne cycloaddition (SPAAC), − native chemical ligation (NCL), , etc., have been successfully used for biolabeling and tracing applications. Recently, increasing reports have demonstrated the utilization of efficient reactions for therapeutic applications by disturbing or blocking the function of biomacromolecules.…”