20465-03-6Relevant articles and documents
Reaction of Boranephosphonate Diesters with Amines in the Presence of Iodine: The Case for the Intermediacy of H-Phosphonate Derivatives
Go??biewska, Justyna,Rachwalak, Marta,Jakubowski, Tomasz,Romanowska, Joanna,Stawinski, Jacek
, p. 5496 - 5505 (2018)
Mechanistic and stereochemical aspects of the reaction of boranephosphonate diesters with amines promoted by iodine were investigated. This is a complex, multistep reaction that ultimately produces the corresponding phosphoramidate diesters via a formal replacement of the borane group by an amine moiety. We found by a stereochemical correlation analysis that, contrary to a literature report, the whole transformation proceeded with total inversion of the configuration at the phosphorus center. Our study also showed that instead of the postulated nucleophilic substitution by iodide at the phosphorus center of the initially formed intermediate, the corresponding iodoboranephosphonate, the crucial step of the reaction involved intermediacy of H-phosphonate derivatives that reacted with iodine to afford ultimately phosphoramidate diesters. The reaction of the iodoboranephosphonate with the amine to produce an aminoboranephosphonate diester that rapidly dissociated into the corresponding H-phosphonate and the borane parts was apparently instrumental to the formation of an H-phosphonate diester intermediate.
The Step-Wise Synthesis of Oligomeric Phosphoramidates
Data, Shailja,Leung Wai, Jeffery,Kumar, Saawan,Cameron, Alan J.,Trehet, Manon,Itumoh, Emeka J.,Feld, Joey,S?hnel, Tilo,Leitao, Erin M.
supporting information, p. 5468 - 5477 (2021/09/30)
In this study, the step-wise synthesis to a series of higher phosphoramidates was explored, affording compounds containing N?P?N, symmetric and asymmetric P?N?P and P?N?P?N?P linkages. Salt elimination and lithiation strategies were employed to create the new P?N bonds. It was found that the steric bulk and electronic contribution of the substituents on the P(V) centers were important factors to the success of the reactions. The oligomeric phosphoramidates were characterized by multinuclear NMR and IR spectroscopies as well as ESI mass spectrometry. A selection of the synthesized P?N oligomers were evaluated for their antimicrobial activity against E.coli, S.aureus, C.albicans, and A.fumigatus at varying concentrations. The results suggest their potential use as environmentally friendly fire retardants as the minimal inhibitory concentration (MIC) value for all the compounds was found to be >128 μM, indicating that the compounds do not have any detectable antimicrobial activity.
Evaluation and development of methodologies for the synthesis of thiophosphinic acids
Winters, Karen R.,Montchamp, Jean-Luc
, p. 14545 - 14558 (2020/12/29)
Thiophosphorus acids R1R2P(S)OH constitute an important class of organophosphorus compounds, in which the phosphorus atom is intrinsically chiral if R1 ≠ R2. In connection with a project aimed at the preparation of chiral thiophosphorus acids, various available literature methods were considered, but few fit the requirement of odorless reagents. Herein, the results of our studies on the synthesis of thiophosphinic acids are reported. Ultimately, two major approaches were selected: (1) the Stec reaction of phosphorus amides with carbon disulfide; and (2) the one-pot synthesis of thiophosphorus acids from H-phosphinates, an organometallic nucleophile, and quenching with elemental sulfur. An application to the preparation of a potential chiral phosphorus organocatalyst is also reported.
An efficient synthesis of phosphoramidates from halides in aqueous ethanol
Dangroo,Dar,Shankar,Khuroo,Sangwan
, p. 2717 - 2722 (2016/06/09)
An environment friendly and efficient synthesis of primary phosphoramidates has been developed from benzyl/allyl/alkyl/propargyl halides in aqueous ethanol as a green reaction medium via in-situ formation of azide. The method is simple, metal free and high yielding at room temperature with wide substrate scope and functional group compatibility. The optimized protocol can be used for synthesis of phosphoramidate intermediates used as prodrug moieties to improve therapeutic potential of the parent drug.
Stereospecific aerobic oxidative dehydrocoupling of P(O)H bonds with amines catalyzed by copper
Zhou, Yongbo,Yang, Jia,Chen, Tieqiao,Yin, Shuang-Feng,Han, Daoqing,Han, Li-Biao
supporting information, p. 400 - 402 (2014/04/17)
Copper-catalyzed stereospecific oxidative dehydrocouplings of P(O)H bonds with amines under air took place effi-ciently at room temperature to afford the corresponding amidophosphorus compounds in high yields. Mechanistic studies showed that this dehydroc
Two-carbon homologation of Grignard reagents to primary amines
Osowska-Pacewicka, Krystyna,Zwierzak, Andrzej
, p. 333 - 335 (2007/10/03)
A novel, convenient synthesis of N-(diethoxyphosphoryl)aziridine is described. Application of this compound as a synthetic equivalent of an a2 type synthon for aminoethylation of Grignard reagents is demonstrated.
Novel organophosphorus reagents for the synthesis of amines
Zwierzak, Andrzej,Osowska-Pacewicka, Krystyna
, p. 569 - 572 (2007/10/03)
New organophosphorus equivalents of a2 type N-protected amine synthons are presented.
THE REACTION OF ETHYL-FORMIMIDATE WITH GRIGNARD REAGENTS: A NEW APPROACH TO ELECTROPHILIC AMINATION
Zawadzki, Stefan
, p. 263 - 268 (2007/10/02)
Addition of Grignard reagents to ethyl-N-(diethoxyphosphoryl)formimidate, 3 followed by aqueous workup and treatment of the resultant diethyl phosphoramidates with p-toluenesulfonic acid in ethanol gives, depending upon the organomagnesium reagent used, the corresponding tosylates of primary or secondary amines in moderate to good yields.The diethoxyphosphoryl moiety remains unchanged upon treatment of 3 with Grignard reagents.Key words: Diethyl-(N-alkylphosphoramidates); Grignard reagents; ammonium tosylates; substitution-addition; substitution-reduction; electrophilic amination.
Direct Conversion of Diethyl Hydrogen Phosphate into Diethyl Phosphoramides
Zwierzak, Andrzej,Osowska-Pacewicka, Krystyna
, p. 117 - 120 (2007/10/02)
The effective, one-step transformation of diethyl hydrogen phosphate into diethyl phosphoramides by using hexamethyltriaminodibromophosphorane prepared "in situ" is described. - Keywords: Hexamethyltriaminodibromophosphorane; Intermolecular dehydration
