Click polymerization

Srinivasachari S, Reineke TM (2009) Versatile supramolecular pDNA vehicles via click polymerization of [beta]-cyclodextrin with oligoethyleneamines. Biomaterials 30 (5) 928—938... 

Scheme 14 Synthesis of /16-PTAs by click polymerization from AB2-type monomers...

Efforts aimed at the synthesis of highly branched polymers have followed two major pathways one directed toward the synthesis of the desired structures by stepwise growth polymerization and another one that uses one-pot or click polymerization of difunctional monomers. 

J.S. Guo, F.B. Meng, X.Y. Li, M.Z. Wang, YJ. Wu, X.B. Jing, Y.B. Huang, PEGylated click polypeptides synthesized by copper-free microwave-assisted thermal click polymerization for selective endotoxin removal from protein solutions, Macromol. Biosci. 12... 

The best example of a click polymerization reaction is the polyaddition reaction of diisocyanates with dioles or polyols to produce polyurethanes. This reaction was discovered... 

Scheme 14.6 Click polymerization of two different [2]pseudorotaxane blocks 11 and 12...

Koyama, Y., Yonekawa,M.,andTakata,T. (2008) New click chemistry click polymerization via 1,3-dipolar addition of homo-ditopic aromatic nitrile oxides formed in situ. Chemistry Letters, 37,918. 

Recently, a Click polymerization strategy has been utilized to produce glycopolymers in which carbohydrates are incorporated into the backbone [198, 199]. Eissa and Khosravi demonstrated the copper wire-catalyzed Click polymerization of di-alkyne-terminated PEG with di-azide-functionalized trehalose prepared by tosylation/acetylation of a,a-D-trehalose followed by azidation reaction (Scheme 12) [199]. The produced alternating linear glycopolymers with triazole linkers were fully characterized and the polymer with a PEG segment of 600 gmol showed a lower critical solution temperature (LCST) at 39°C, which is known as the fever temperature. This material constituted a new class of temperature-responsive water-soluble glycopolymers. 

Figure 8.3 Synthesis of linear polymers by thiol-epoxy click" polymerization.

Ihomson1- W Click Organic Interactive to predict products from simple polymerization reactions. 

Xiao CS, Zhao CW, He P, Tang ZH, Chen XS, Jing XB (2010) Facile synthesis of glycopo-lypeptides by combination of ring-opening polymerization of an alkyne-substituted N-carboxyanhydride and click glycosylation . Macromol Rapid Commun 31 991-997... 

Huang J, Habraken G, Audouin F, Heise A (2010) Hydrolytically stable bioactive synthetic glycopeptide homo- and copolymers by combination of NCA polymerization and click reaction. Macromolecules 43 6050-6057... 

Finally, Lecomte and coworkers reported the synthesis of mikto-arm star-shaped aliphatic polyesters by implementing a strategy based on click chemistry (Fig. 36) [162]. Firstly, the polymerization of sCL was initiated by a diol bearing an alkyne function. The chain-ends were protected from any further undesired reaction by the esterification reaction with acetyl chloride. The alkyne was then reacted with 3-azidopropan-l-ol. The hydroxyl function located at the middle of the chain was then used to initiate the ROP of sCL and y-bromo-s-caprolactone. Finally, pendant bromides were reacted successfully with sodium azide and then with N, N-dimethylprop-2-yn-l-amine to obtain pendant amines. Under acidic conditions, pendant amines were protonated and the polymer turned out to exhibit amphiphilic properties. 

Riva R, Schmeits S, Jerome C, Jerome R, Lecomte P (2007) Combination of ring-opening polymerization and click chemistry toward functionalization and grafting of poly( -caprolactone). Macromolecules 40 796-803... 

Another approach, which does not make use of either free or controlled radical polymerization, was demonstrated by Parrish et al. [20]. An aliphatic polyester with pendent acetylene groups was prepared via controlled ring-opening polymerization. Polyethylene glycol and the peptide sequence Gly - Arg - Gly - Asp - Ser (GRGDS) were functionalized with an azide moiety, and subsequently clicked to the pendent acetylenes in the... 

Alkene-functionalized linear polymers, such as the polyether-thioether described in Figure 3.9, was prepared by thiol-ene click step-growth polymerization using a fast, efficient, and green approach for the synthesis of macromonomers with a variety of functionalities. 

The modification of polymers can be readily conducted by chemical coupling reactions when the chain to be modified possesses groups such as vinyl, hydroxyl, or azide [23], etc. The Diels-Alder reaction between a diene and a dienophile, discovered by Otto Diels and Kurt Alder in 1928 [24], is the most important example of click chemistry. These robust and efficient click coupling reactions have been widely exploited in the construction of tailor-made functional polymeric materials with complex molecular architectures... 

Tsarevsky has found that hypervalent iodine compounds can be used for the direct azidation of polystyrene and consecutive click-type functionalization [49]. In particular, polystyrene can be directly azidated in 1,2-dichloroethane or chlorobenzene using a combination of trimethylsilyl azide and (diacetoxyiodo)benzene. 2D NMR HMBC spectra indicate that the azido groups are attached to the polymer backbone and also possibly to the aryl pendant groups. Approximately one in every 11 styrene units can be modified by using a ratio of PhI(OAc)2 to trimethylsilyl azide to styrene units of 1 2.1 1 at 0 °C for 4 h followed by heating to 50 °C for 2 h in chlorobenzene. The azidated polymers have been further used as backbone precursors in the synthesis of polymeric brushes with hydrophilic side chains via a copper-catalyzed click reaction with poly(ethylene oxide) monomethyl ether 4-pentynoate [49],... 

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