Ferrocene-based P-chiral amidophosphinate: stereoselective synthesis and X-ray structural study

Racemic and enantiopure ferrocene-based P-chiral amidophosphinates have been simply and stereoselectively synthesized by ortho-lithiation of rac- or (R)-Ugi's amine and further reaction with amidochlorophenylphosphinate Cl-P(O)(Ph)NEt2. This is the first example of an asymmetric reaction of ortho-lithiated Ugi's amine with tetracoordinated phosphorus(v) chlorides. The structures of rac- and (R)-Ugi's amine ferrocenyl(phenyl)phosphinic acid N,N-diethylamide have been extensively studied experimentally (NMR, X-ray analysis, electrochemistry). The CV first peak refers to the oxidation of the amine fragment, which is clearly seen when (R)-Ugi's amine ferrocenyl(phenyl)phosphinic acid N,N-diethylamide reacts with anhydrous acid. The addition of two equivalents of CF3COOH leads to the protonation of nitrogen atoms, and a classical reversible wave of oxidation of Fe(ii) to Fe(iii) is observed.

Automated summary

In this study, racemic and enantiopure ferrocene-based P-chiral amidophosphinates were synthesized by ortho-lithiation reaction and reaction with amidochlorophenylphosphinate. The structures of the synthesized compounds were analyzed experimentally, and the oxidation and reduction reactions were observed.