Jagannathan Jake R, Targos Karina, Franz Annaliese K
Department of Chemistry, University of California, Davis, One Shields Avenue, Davis, CA, USA.
Angew Chem Int Ed Engl. 2022 Jan 3;61(1):e202110417. doi: 10.1002/anie.202110417. Epub 2021 Nov 22.
We report carbene insertion into Si-H bonds of polyhedral oligomeric silsesquioxanes (POSS) for the synthesis of highly functionalized siloxane nanomaterials. Dirhodium(II) carboxylates catalyze insertion of aryl-diazoacetates as carbene precursors to afford POSS structures containing both ester and aryl groups as orthogonal functional handles for further derivatization of POSS materials. Four diverse and structurally varied silsesquioxane core scaffolds with one, three, or eight Si-H bonds were evaluated with diazo reactants to produce a total of 20 new POSS compounds. Novel diazo compounds containing a fluorinated octyl group and boron-dipyrromethene (BODIPY) chromophore demonstrate the use of highly functionalized substrates. Transformations of aryl(ester)-functionalized POSS compounds derived from this method are demonstrated, including ester hydrolysis and Suzuki-Miyaura cross-coupling.
我们报道了通过卡宾插入多面体低聚倍半硅氧烷（POSS）的Si-H键来合成高度官能化的硅氧烷纳米材料。羧酸二铑（II）催化作为卡宾前体的芳基重氮乙酸酯的插入反应，以得到同时含有酯基和芳基的POSS结构，作为POSS材料进一步衍生化的正交官能团。使用具有一个、三个或八个Si-H键的四种不同且结构各异的倍半硅氧烷核心支架与重氮反应物进行反应，总共制备了20种新的POSS化合物。含有氟化辛基和硼二吡咯亚甲基（BODIPY）发色团的新型重氮化合物展示了高官能化底物的应用。通过该方法得到的芳基（酯）官能化POSS化合物的转化反应也得到了证实，包括酯水解和铃木-宫浦交叉偶联反应。
