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.
Bauer
Ingmar
I
Institute of Organic Chemistry, University of Technology Dresden, Mommsenstrasse 13, 01062 Dresden, Germany. ingmar.bauer@chemie.tu-dresden.de
Gruner
Margit
M
Goutal
Sigrid
S
Habicher
Wolf D
WD
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