181480-95-5Relevant academic research and scientific papers
Lithium Borohydride for Achiral and Stereospecific Reductive Boronation at Phosphorus: Lack of Electronic Effects on Stereoselective Formation of Alkoxyphosphonium Salts
Al Sulaimi, Sulaiman S.,Rajendran, Kamalraj V.,Gilheany, Declan G.
supporting information, p. 5959 - 5965 (2015/09/22)
We report LiBH4 as a preferred, simple and effective reagent for reductive boronation of achiral and racemic chlorophosphonium salts (CPS) and for diastereomeric alkoxyphosphonium salts (DAPS), both of which are, in turn, easily generated from either the corresponding phosphane or, more conveniently, the phosphane oxide. Further, we have shown that the DAPS reduction/boronation could be achieved with complete stereocontrol to give scalemic phosphane-borane directly in excellent yield and enantiomeric excess (ee). This new methodology was employed to investigate the effects of aryl substitution on the outcome of dynamic kinetic resolution of arylmethylphenylphosphanes and phosphane oxides via DAPS. It was found that substitution at the ortho position strongly affects the degree of stereoselection. However, surprisingly, we confirmed that there was no variation of stereoselectivity seen with the electronic effect of substituents on the para position.
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.
PROCESSES FOR THE STEREOSELECTIVE PREPARATION OF P-CHIRAL FOUR -COORDINATED PHOSPHORUS BORANE COMPOUNDS AND P-CHIRAL THREE-COORDINATED PHOSPHORUS COMPOUNDS
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Page/Page column 64, (2012/09/11)
Processes for the stereoselective preparation of P-chiral four-coordinated phosphorus borane compounds and P-chiral three-coordinated phosphorus compounds.
Simple unprecedented conversion of phosphine oxides and sulfides to phosphine boranes using sodium borohydride
Rajendran, Kamalraj V.,Gilheany, Declan G.
, p. 817 - 819 (2012/02/03)
A variety of phosphine oxides and sulfides can be efficiently converted directly to the corresponding phosphine boranes using oxalyl chloride followed by sodium borohydride. Optically active P-stereogenic phosphine oxides can be converted stereospecifically to phosphine boranes with inversion of configuration by treatment with Meerwein's salt followed by sodium borohydride.
