35671-02-4Relevant academic research and scientific papers
Systematic study for the stereochemistry of the Atherton-Todd reaction
Xiong, Biquan,Zhou, Yongbo,Zhao, Changqiu,Goto, Midori,Yin, Shuang-Feng,Han, Li-Biao
, p. 9373 - 9380 (2013/10/08)
Under the Atherton-Todd reaction conditions, the stereochemistry on the reaction of H-phosphinates with different nucleophiles (e.g., amines, alcohols, phenols) was investigated. All reactions took place stereospecifically with inversion of configurations at the phosphorus centers. The reaction might proceed via a phosphoryl chloride intermediate with retention of configuration at phosphorus, followed by the attack of nucleophiles from the backside of Cl to give the substitution products with inversion of configuration at the phosphorus center. A plausible mechanism was proposed for these reactions.
Stereospecific coupling of H -phosphinates and secondary phosphine oxides with amines and alcohols: A general method for the preparation of optically active organophosphorus acid derivatives
Wang, Gang,Shen, Ruwei,Xu, Qing,Goto, Midori,Zhao, Yufen,Han, Li-Biao
supporting information; experimental part, p. 3890 - 3892 (2010/07/05)
Figure presented The reaction of H-phosphinates and secondary phosphine oxides with amines and alcohols proceeds highly stereospecifically to give the corresponding coupling products with inversion of configuration at the phosphorus center under the Atherton-Todd reaction conditions. This finding leads to the establishment of a general and efficient method for the synthesis of a variety of optically active organophosphorus acid derivatives from the easily available chiral H-phosphinates and secondary phosphine oxides.
Stereospecific halogenation of P(O)-H bonds with copper(II) chloride affording optically active Z1Z2P(O)Cl
Zhou, Yongbo,Wang, Gang,Saga, Yuta,Shen, Ruwei,Goto, Midori,Zhao, Yufen,Han, Li-Biao
scheme or table, p. 7924 - 7927 (2011/02/23)
A general and efficient method for the preparation of optically active Z1Z2P(O)Cl from the easily prepared optically active H-phosphinates and H-phosphine oxides was reported. H-Phosphinates and H-phosphine oxides react stereospecifi
SILICON-PHOSPHORUS ANALOGIES. PARTICIPATION OF EXTERNAL NUCLEOPHILES TO ACTIVATED PROCESSES OF RACEMIZATION AND HYDROLYSIS OF CHLOROPHOSPHONO DERIVATIVES
Corriu, R. J. P.,Lanneau, G. F.,Leclercq, D.
, p. 1617 - 1626 (2007/10/02)
Kinetic and stereochemical studies show nucleophilic assistance by dimethylformamide (DMF), dimethylacetamide (DMA), hexamethylphosphotriamide (HMPT) and N-methylimidazole (NMI) in racemization and solvolysis of menthylchloro(phenyl)phosphonate, 1a, and O-ethylchloro(phenyl)thiophosphonate, 2.Similar orders of nucleophilic reactivity (Nu = NMI >> HMPT > DMF> DMA), and identical rate laws (vrac = k 2 and vH2O = k') are consistent with a common mechanism, governed by entropy (-60 u.e/= -40 u.e.).Analogies between reaction mechanisms at silicon and phosphorus are clearly evidenced.A two step process, involving rate-determining attack on a pentacoordinate complex is discussed.
