ChemInform Abstract: PHOTOLYSIS OF FLUOROSULFONYLDIFLUOROACETYL CHLORIDE

Octakis(3‐azidopropyl)octasilsesquioxane: A Versatile Nanobuilding Block for the Efficient Preparation of Highly Functionalized Cube‐Octameric Polyhedral Oligosilsesquioxane Frameworks Through Click Assembly

“…Compound 5 is commercially available as its octahydrochloride salt6 and can be easily obtained in multigram quantities from an inexpensive organosilicon precursor 19. 20, 38 We examined two different diazo‐transfer reagents for the synthesis of 6 : trifluoromethanesulfonyl (triflyl) azide, which has often been used for the preparation of organic azides from the corresponding primary amines, mostly in carbohydrate chemistry;69–71 and nonafluorobutanesulfonyl (nonaflyl) azide,72, 73 which at the onset of our work had never been used before for the synthesis of organic azides 74. Triflyl azide is potentially explosive, it has a relatively poor shelf life and it must be prepared just before use from triflic anhydride and sodium azide as a solution in dichloromethane69, 75 or toluene 76.…”

“…Triflyl azide is potentially explosive, it has a relatively poor shelf life and it must be prepared just before use from triflic anhydride and sodium azide as a solution in dichloromethane69, 75 or toluene 76. In contrast, nonaflyl azide is stable at room temperature, can be safely distilled and kept as a neat reagent at 4 °C for later use without decomposition, and is easily obtained from the much cheaper and readily available nonaflyl fluoride 72. 73 In an initial screening of reaction conditions (Table 1), we identified two factors that were critical to obtain an optimal yield of 6 .…”