ChemInform Abstract: Experimental and Theoretical Investigations of the Stereoselective Synthesis of P‐Stereogenic Phosphine Oxides.

Abstract

Experimental and Theoretical Investigations of the Stereoselective Synthesis of P-Stereogenic Phosphine Oxides. -The cyclization of aminocyclohexanol (II) with Ph-POCl 2 (I) followed by cleavage of P-N bond in the intermediate oxazaphospholidine with Grignard reagents (III) leads to phosphinates (IV), which are converted into (S)-phosphine oxides (VI) by refluxing with a second Grignard reagent in THF. Opposite enantiomers (R)-(VI) are prepared by reaction of Ph-PCl2 with aminocyclohexanol (II), cleavage of P-N in the intermediate oxazaphospholidine, phosphine oxidation with H 2O2, and subsequent P-O bond cleavage with MeMgCl (IIIa). -(COPEY, L.; JEAN-GERARD, L.; FRAMERY, E.; PILET, G.; ROBERT, V.; ANDRIOLETTI*, B.; Chem. -Eur. J. 21 (2015) 25, 9057-9061, http://dx.doi.org/10.1002/chem.201501324 ; Inst. Chim. Biochim. Mol. Supramol., Univ. Claude Bernard Lyon, F-69622 Villeurbanne, Fr.; Eng.) -R. Staver 44-206