Instituto de Química Orgánica General, CSIC, Juan de La Cierva, 3, 28006 Madrid, Spain.
Chemistry. 2010 Mar 22;16(12):3833-41. doi: 10.1002/chem.200902422.
A one-step synthesis of octakis(3-azidopropyl)octasilsesquioxane from commercially available octakis(3-aminopropyl)octasilsesquioxane has been developed through a highly efficient diazo-transfer reaction under very mild conditions. Nonaflyl azide is shown to be a safer, cheaper, and more efficient reagent for this transformation than the better known and generally used diazo-transfer reagent triflyl azide. Octakis(3-azidopropyl)octasilsesquioxane is an excellent nanobuilding block that can be readily octafunctionalized with a range of terminal alkynes by copper(I)-catalyzed 1,3-dipolar azide-alkyne cycloaddition to provide new functional nanocages, maintaining a perfect 3D cubic symmetry. The mildness, simplicity, and efficiency of this approach have been demonstrated in the preparation of a glyco-polyhedral oligosilsesquioxane (POSS) conjugate and a BODIPY-POSS cluster (BODIPY = boron dipyrromethene).
通过在非常温和的条件下进行高效的重氮转移反应，从商业可得的八（3-氨丙基）倍半硅氧烷一步合成了八（3-叠氮丙基）倍半硅氧烷。与更知名且通常使用的重氮转移试剂三氟甲磺酸叠氮相比，非氟叠氮化物被证明是这种转化的更安全、更便宜、更有效的试剂。八（3-叠氮丙基）倍半硅氧烷是一种极好的纳米构建块，通过铜（I）催化的 1,3-偶极叠氮化物-炔烃环加成反应，可轻松与一系列末端炔烃进行八官能化，提供新的功能纳米笼，保持完美的 3D 立方对称性。该方法的温和性、简单性和高效性已在糖多面体低聚倍半硅氧烷（POSS）缀合物和 BODIPY-POSS 簇（BODIPY = 硼二吡咯甲烷）的制备中得到证明。
