Staudinger Reaction at in‐Bridgehead Positions of Phosphorus Macrobicyclic Compounds

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 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.

Phosphorus-containing macrocyclic compounds: synthesis and properties

“…27,42 The cavity in in,in-phosphite 47 is apparently too small for the reaction of thiophosphoryl azide 49 to proceed at both in positions, due to which monosubstituted cryptand 51 is formed as the major product. In this case, the partial thionation of the starting phosphite and the product to form compounds 50 and 52, respectively, are side reactions.…”

Synthesis of arylenephosphamacrocycles using tri- and pentavalent phosphorus compounds

“…27 The synthesis and investigations of the chemical features of cyclic phosphites and phosphorus-containing cryptands have been well documented in a review. 28 At present, cyclophosphorylation reactions are carried out using phosphorochloridites and phosphoramidites, the latter often being more convenient because they react with phenols at room temperature in various solvents and do not require removal of amines released.…”

17 Macrocyclic coordination chemistry

“…This will allow the introduction of a range of groups into the cavity to allow its size and guest binding properties to be tailored. 38 The selection of a pentameric phosphorus donor host in the assembly of cyclic phosphazenes is a kinetic template effect, arising from the presence of chloride ion, which is nicely encapsulated by hydrogen bonding in its adduct with the cyclic pentamer. 39 An interesting metallomacrocycle with a 1,3-alternate calix [4]arene phosphorus ligand has also been prepared.…”