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 Cs-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 C3v 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.
Institute of Organic Chemistry, University of Technology Dresden, Mommsenstrasse 13, 01062 Dresden, Germany. ingmar.bauer@chemie.tu-dresden.de
Ingmar
I
Bauer
Margit
M
Gruner
Sigrid
S
Goutal
Wolf D
WD
Habicher
D018360:Crystallography, X-Ray; D047028:Macrocyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D046911:Macromolecular Substances / Q000138:chemical synthesis* / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D009943:Organophosphorus Compounds / Q000138:chemical synthesis* / Q000737:chemistry
D047028:Macrocyclic Compounds; D046911:Macromolecular Substances; D009943:Organophosphorus Compounds