Nouveaux Macrocycles Bicyclophosphoraniques Ii Macrocycles Mixtes Dérivant De 3-Oxo, 3-Amino Et 3-Thio- 1,5-Pentanediols

Amides of Trivalent Phosphorus Acids as Phosphorylating Reagents for Proton-Donating Nucleophiles

“…Even in the first study dealing with the alcoholysis and phenolysis of simple ATPA, an “addition−elimination” mechanism was proposed for this reaction (Scheme ). Later, the possibility of the formation of hydrophosphoranes has been confirmed experimentally in studies dealing with some cyclic systems. − Simultaneously, a mechanism based on the formation of a four-membered transition state has been proposed for the alcoholysis of ATPA, but this has not been confirmed experimentally.

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“…Many researchers have expressed opinions on the mechanism of ATPA transamidation and on the dependence of the ease of the reaction on the substrate and reagent structures, which were based either on their observations or on general considerations. A scheme has been proposed that included mutual addition of the phosphamide and amine to give a phosphorane and decomposition of the latter to give the reaction products (Scheme ). ,,,,

86

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“…Later, the possibility of the formation of hydrophosphoranes has been confirmed experimentally in studies dealing with some cyclic systems. [7][8][9][10][11][12][13][14] Simultaneously, a mechanism based on the formation of a four-membered transition state has been proposed for the alcoholysis of ATPA, 15 but this has not been confirmed experimentally.…”

“…A scheme has been proposed that included mutual addition of the phosphamide and amine to give a phosphorane and decomposition of the latter to give the reaction products (Scheme 86). 12,34,158,493,494 Mechanisms including a four-membered transition state 15 and those based on direct nucleophilic substitution at the phosphorus atom have also been discussed. The latter version is encountered most frequently in standard reactions.…”