Staudinger Reaction at in ‐Bridgehead Positions of Phosphorus Macrobicyclic Compounds

Reaction of in , in ‐phosphite 1 with thiophosphoryl azide 2 affords in , in ‐dithiophosphate 3 , in , in ‐thiophosphate–imidophosphate 4 , and in , in ‐phosphite–imidophosphate 5 . Compounds 4 and 5 are the first examples of the modification of in ‐bridgehead positions in macrobicyclic compounds with groups larger than methyl. The benzaldehyde arms of the in ‐substituent in 4 and 5 jut out of the cage bars. In 4 they are trapped between the macrocyclic arms to give the NMR spectra of a C s ‐symmetric solution‐state structure. In contrast, in 5 the benzaldehyde arms can move between the gaps of the cage. This results in 1 H and 13 C NMR spectra which are consistent for a compound with C 3 v symmetry. In , out ‐diimidophosphate 7 is obtained in moderate yield by reaction of in , out ‐phosphite 6 with thiophosphoryl azide 2 . Its in ‐benzaldehyde moieties are not fixed between the cage arms, but can freely move from one gap to the next as is indicated by NMR measurements.