138079-34-2Relevant academic research and scientific papers
Reactivity of Ferrocenyl Phosphates Bearing (Hetero-)Aromatics and [3]Ferrocenophanes toward Anionic Phospho-Fries Rearrangements
Korb, Marcus,Lehrich, Steve W.,Lang, Heinrich
, p. 3102 - 3124 (2017)
The temperature-dependent behavior within anionic phospho-Fries rearrangements (apFr) of P(O)(OFc)n(EAr)3-n (Fc = Fe(η5-C5H5)(η5-C5H4); E = O; Ar = phenyl, naphthyls, (R)-BINOL, [3]ferrocenophanyl; E = N, 1H-pyrrolyl, 1H-indolyl, 9H-carbazolyl; n = 1-3) is reported. While Fc undergoes one, the Ph-based apFr depends on temperature. First, the aryls are lithiated and rearranged, followed by Fc and N-heterocycles. Addition of Me2SO4 thus gave methylated Fc, contrary to non-organometallic aromatics giving mixtures of HO and MeO derivatives. The (R)-BINOL Fc phosphate gave Fc-rearranged phosphonate in 91% de. Exchanging O- with N-aliphatics prevented apFr, due to higher electron density at P. Also 1,2-N→C migrations were observed. X-ray analysis confirms 1D H bridge bonds for OH and NH derivatives. The differences in reactivity between N-aliphatic and N-aromatic phosphoramidates were verified by electrochemistry. The redox potentials revealed lower values for the electron-rich aliphatics, showing no apFr, preventing a nucleophilic attack at P after lithiation. Redox separations for multiple Fc molecules are based on electrostatic interactions.
PYROCATECHOL CYCLOPHOSPHATES IN REACTIONS WITH PROTON-CONTAINING NUCLEOPHILES
Nifant'ev, E. E.,Kukhareva, T. S.,Soldatova, I. A.,Matrosov, E. I.
, p. 1209 - 1212 (2007/10/02)
A general principle of the hydrolysis and alcoholysis of cyclophosphates of pyrocatechol and its derivatives is facile ring opening and anomalously facile cleavage of the P-O (P-N) bond to give, in all of the indicated cases, phosphoric acid 2-hydroxyphenyl phosphate.The latter is predetermined by the formation of a hydrogen bond with the participation of the phenolic hydroxy group of the 2-hydroxyphenyl radical.
