Copper-Catalyzed vs Thermal Step Growth Polymerization of Starch-Derived α-Azide-ω-Alkyne Dianhydrohexitol Stereoisomers: To Click or Not To Click?

被引：68

作者：

Besset, Celine ^{[1
,2
]}

Binauld, Sandra ^{[1
]}

Ibert, Mathias ^{[2
]}

Fuertes, Patrick ^{[2
]}

Pascault, Jean-Pierre ^{[1
]}

Fleury, Etienne ^{[1
]}

Bernard, Julien ^{[1
]}

Drockenmuller, Eric ^{[1
]}

机构：

[1] Univ Lyon 1, INSA Lyon, IMP UMR 5223, CNRS, F-69622 Villeurbanne, France

[2] Roquette Freres, Div Rech, F-62080 Lestrem, France

来源：

MACROMOLECULES | 2010年 / 43卷 / 01期

关键词：

1,3-DIPOLAR CYCLOADDITION; TERMINAL ALKYNES; CHEMISTRY; POLYMERS; UNITS;

D O I：

10.1021/ma9024784

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

The synthesis of α-azide-ω-alkyne 1,4:3,6-dianhydrohexitols with controlled stereochemistry from starch-derived isosorbide, isomannide, and isoidide as well as a detailed study of their polyaddition by CuAAC in solution or by catalyst and solvent-free 1,3-dipolar Huisgen cycloaddition, was reported. α-Azide-ω-alkyne dianhydrohexitol stereoisomers 9-12 (RR, RS, SR, SS) were obtained from isosorbide, isoidide, and isomannide using a three-step synthetic pathway. Alkylation of the remaining hydroxyl group by propargyl bromide was then performed at room temperature to avoid any undesirable step growth polymerization. Monomers 9-12 were stored at -20°C, a temperature below which no traces of coupling products could be observed by 1H NMR after several months of storage. The regioselectivity of the CuAAC step growth polymerization was clearly demonstrated by 1H NMR with the appearance of a single signal at 8.16 ppm characteristic of 1,4-disubstituted 1,2,3-triazoles.

引用

页码：17 / 19

页数：3

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