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.
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.
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
