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Updated: Jun 22, 2026

Design, Synthesis, and Photochemical Properties of Clickable Caged Compounds
Published on: October 15, 2019
Controllable selective functionalization of a cavitand via solid state photolysis of an encapsulated phenyl azide
Gerald Wagner1, Vladimir B Arion, Lothar Brecker
1Institute of Organic Chemistry, University of Vienna, Wahringer Strasse 38, A-1090 Vienna, Austria.
Abstract:
Phenyl azide (1) has been encapsulated within cavitand 2 to form a 1:1 complex of 1@2 in the solid state. Subsequent irradiation affords two diastereomeric nitrene addition products 5 and 7. The ratio of 5 and 7 can be reversed by thermally induced valence isomerization to 1H-azepine 8 followed by photolysis. In sharp contrast, phenylnitrene generation by photolysis of the corresponding 1.5:1 complex results mainly in the regioselective formation of C-H insertion product 4. The supramolecular approach to phenylnitrene chemistry provides good yields, in contrast to the generally low yield reactions of this species in solution.
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