Staudinger Reaction at in-Bridgehead Positions of Phosphorus Macrobicyclic Compounds
✍ Scribed by Ingmar Bauer; Margit Gruner; Sigrid Goutal; Wolf D. Habicher
- Publisher
- John Wiley and Sons
- Year
- 2004
- Tongue
- English
- Weight
- 245 KB
- Volume
- 10
- Category
- Article
- ISSN
- 0947-6539
No coin nor oath required. For personal study only.
✦ Synopsis
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.