98643-06-2Relevant articles and documents
Reinvestigation of the iodine-mediated phosphoramidation reaction of amines and P(OR)3 and its synthetic applications
Chen, Xunwei,Xiao, Zecai,Chu, Hanyu,Wang, Bo,Peng, Ai-Yun
, p. 6783 - 6790 (2018/09/29)
A systematic study on the iodine-mediated phosphoramidation reaction of amines and trialkyl phosphites was conducted, which not only disclosed the factors affecting the reaction but also revealed that it could proceed smoothly in CH2Cl2 at room temperature in open air. Using this method, various phosphoramidates with different aliphatic amines and aromatic amines were synthesized in good to excellent yields. Our present investigation shows that this underused method is actually a mild, practical and general way to synthesize phosphoramidates and will have wide applications.
Transformation of Arylmethylamines into α-Aminophosphonic Acids via Metalated Phosphoramidates: Rearrangement of Partly Configurationally Stable N-Phosphorylated α-Aminocarbanions
Hammerschmidt, Friedrich,Hanbauer, Martin
, p. 6121 - 6131 (2007/10/03)
N-Benzyl phosphoramidate was protected at nitrogen with a TMS, p-toluenesulfonyl, Boc, lithium carboxylate, or diethoxyphosphinyl group and metalated with s-BuLi or LDA at -78 °C at the benzylic carbon. For the latter three protecting groups, the intermediate α-amino(phenylmethyl)-lithiums isomerized to N-protected α-aminophosphonates (phosphoramidate-aminophosphonate rearrangement). (R)-N-[1-2H1]Phenylmethyl phosphoramidate in combination with Boc or (EtO)2P-(O) was used to demonstrate that metalation occurs with a high primary kinetic isotope effect (kH/kD 13-50) and migration of the diethoxyphosphinyl group with retention of configuration at carbon. Furthermore, the short-lived carbanion lithium pairs are partly configurationally stable as the aminophosphonates formed with the two protecting groups have enantiomeric excesses of 79 and 24%, respectively. When homochiral lithium amides derived from (R)-N-isopropyl-1-phenylethylamine and (R,R)-N,N-di(1-phenylethyl)amine were used to induce a phosphoramidate-aminophosphonate rearrangement, chiral nonracemic α-aminophosphonates were formed (ee 26-35%). Three racemic aminophosphonates were deprotected with hot 6 M HCl and purified by ion-exchange chromatography on Dowex 50W,H+ to exemplify the transformation of phenyl-, p-tolyl-, and (1′-naphthyl)methylamine into aminophosphonic acids via lithiated phosphoramidates.
