Controllable selective functionalization of a cavitand via solid state photolysis of an encapsulated phenyl azide.
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.
Wagner
Gerald
G
Institute of Organic Chemistry, University of Vienna, Wahringer Strasse 38, A-1090 Vienna, Austria.
Arion
Vladimir B
VB
Brecker
Lothar
L
Krantz
Carsten
C
Mieusset
Jean-Luc
JL
Brinker
Udo H
UH