Abstract

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 ¹H and ¹³C NMR spectra which are consistent for a compound with C_3v 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.