Click Chemistry on Surfaces: 1,3-Dipolar Cycloaddition Reactions of Azide-Terminated Monolayers on Silica
Click Chemistry on Surfaces: 1,3-Dipolar Cycloaddition Reactions of Azide-Terminated Monolayers on Silica
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DOI：
10.1021/jp049601t
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发表时间：
2004-03
影响因子：
3.3
通讯作者：
T. Lummerstorfer;H. Hoffmann
中科院分区：
文献类型：
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作者：
T. Lummerstorfer;H. Hoffmann
通过取代11-溴-十一烷基硅氧烷，在粉末二氧化硅和硅片上制备11-叠氮基-十一烷基硅氧烷单层，然后通过Huisgen 1，3-偶极环加成反应与三个取代的乙炔R-C-C-R '（R，R' = C6 H1, 3，H（1）; COOCH 3，H（2）; COOC 2 H5，COOC 2 H5（3））偶联，得到1，2，3-三唑。通过红外光谱和椭圆偏振仪监测表面反应的途径和产率。未观察到与1的反应，而2和3在70 °C的温度下在粉末状二氧化硅和平坦晶片表面上定量反应而无催化活化。因此，该反应在溶液中的独特性质（高选择性，定量产率，无副产物，简单的反应条件）似乎是可转移到表面结合的反应物，并可能提供一系列的新颖的，功能化的表面通过类比夏普斯点击化学概念的溶液相合成。
Monolayers of 11-azido-undecylsiloxane were prepared on powdered silica and on silicon wafers by the substitution of 11-bromo-undecylsiloxane and were subsequently coupled with three substituted acetylenes R−C⋮C−R‘ (R, R‘ = C6H13, H (1); COOCH3, H (2); COOC2H5, COOC2H5 (3)) to yield 1,2,3 triazoles via the Huisgen 1,3-dipolar cycloaddition reaction. The pathway and yield of the surface reactions were monitored by infrared spectroscopy and ellipsometry. No reaction was observed with 1, whereas 2 and 3 react quantitatively both on powdered silica and on flat wafer surfaces at a temperature of 70 °C without catalytic activation. Thus, the unique properties of this reaction in solution (high selectivity, quantitative yields, no byproducts, simple reaction conditions) seem to be transferable to surface-bound reactants and might provide access to a range of novel, functionalized surfaces by analogy to the Sharpless click chemistry concept for solution-phase synthesis.