98934-00-0Relevant academic research and scientific papers
Method for manufacturing a new dephosphorizing ligand homochiral (by machine translation)
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, (2016/10/10)
Disclosed are methods for making chiral phosphorus ligands including chiral phosphines, chiral phosphine oxides, phosphonamides, and aminophosphines. The chiral phosphorus ligands prepared by the methods of the invention are useful as components of chiral catalysts, e.g., transition metal complexes.
Catalyzing pyramidal inversion: Configurational lability of P-stereogenic phosphines via single electron oxidation
Reichl, Kyle D.,Ess, Daniel H.,Radosevich, Alexander T.
supporting information, p. 9354 - 9357 (2013/07/25)
We report that pyramidal inversion of trivalent phosphines may be catalyzed by single electron oxidation. Specifically, a series of P-stereogenic (aryl)methylphenyl phosphines are shown to undergo rapid racemization at ambient temperature when exposed to catalytic quantities of a single electron oxidant in solution. Under these conditions, transient phosphoniumyl radical cations (R3P?+) are formed, and computational models indicate that the pyramidal inversion barriers for these open-shell intermediates are on the order of ～5 kcal/mol. The observed 1020-fold rate enhancement over uncatalyzed pyramidal inversion opens new opportunities for the dynamic stereochemistry of phosphines and may hold additional implications for the configurational stability of P-stereogenic phosphine ligands on high-valent oxidizing transition metals.
Efficient asymmetric synthesis of P -chiral phosphine oxides via properly designed and activated benzoxazaphosphinine-2-oxide agents
Han, Zhengxu S.,Goyal, Navneet,Herbage, Melissa A.,Sieber, Joshua D.,Qu, Bo,Xu, Yibo,Li, Zhibin,Reeves, Jonathan T.,Desrosiers, Jean-Nicolas,Ma, Shengli,Grinberg, Nelu,Lee, Heewon,Mangunuru, Hari P. R.,Zhang, Yongda,Krishnamurthy, Dhileep,Lu, Bruce Z.,Song, Jinhua J.,Wang, Guijun,Senanayake, Chris H.
, p. 2474 - 2477 (2013/03/28)
A general, efficient, and highly diastereoselective method for the synthesis of structurally and sterically diverse P-chiral phosphine oxides was developed. The method relies on sequential nucleophilic substitution on the versatile chiral phosphinyl transfer agent 1,3,2-benzoxazaphosphinine-2-oxide, which features enhanced and differentiated P-N and P-O bond reactivity toward nucleophiles. The reactivities of both bonds are fine-tuned to allow cleavage to occur even with sterically hindered nucleophiles under mild conditions.
A NEW METHOD FOR THE SYNTHESIS OF OPTICALLY PURE PHOSPHINE OXIDES
Imamoto, Tsuneo,Sato, Kazuhiko,Johnson, Carl R.
, p. 783 - 786 (2007/10/02)
Tertiary phosphine oxides have been prepared with high enantiomeric excesses via intermediate menthyl 2-phosphinylacetates.
