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Staudinger Reaction at in ‐Bridgehead Positions of Phosphorus Macrobicyclic Compounds
Author(s) -
Bauer Ingmar,
Gruner Margit,
Goutal Sigrid,
Habicher Wolf D.
Publication year - 2004
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200400204
Subject(s) - thiophosphate , benzaldehyde , chemistry , substituent , azide , yield (engineering) , nmr spectra database , polymer chemistry , medicinal chemistry , spectral line , organic chemistry , catalysis , materials science , physics , metallurgy , astronomy
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 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.