title: Experimental and theoretical investigations of the stereoselective synthesis of p-stereogenic phosphine oxides.
abstract: An efficient enantioselective strategy for the synthesis of variously substituted phosphine oxides has been developed, incorporating the use of (1S,2S)-2-aminocyclohexanol as the chiral auxiliary. The method relies on three key steps: 1) Highly diastereoselective formation of P(V) oxazaphospholidine, rationalized by a theoretical study; 2) highly diastereoselective ring-opening of the oxazaphospholidine oxide with organometallic reagents that takes place with inversion of configuration at the P atom; 3) enantioselective synthesis of phosphine oxides by cleavage of the remaining P-O bond. Interestingly, the use of a P(III) phosphine precursor afforded a P-epimer oxazaphospholidine. Hence, the two enantiomeric phosphine oxides can be synthesized starting from either a P(V) or a P(III) phosphine precursor, which constitutes a clear advantage for the stereoselective synthesis of sterically hindered phosphine oxides.
authors.affiliation: Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS-UMR CNRS 5246), Université Claude Bernard Lyon 1, Bâtiment Curien (CPE) 43, Bd du 11 Novembre 1918, 69622 Villeurbanne cedex (France), Fax: (+33) 472-44-6264 http://www.icbms.fr/casyen/45-casyen-andrioletti/23-andrioletti.
authors.forename: Laurent
authors.initials: L
authors.lastname: Copey
authors.affiliation: Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS-UMR CNRS 5246), Université Claude Bernard Lyon 1, Bâtiment Curien (CPE) 43, Bd du 11 Novembre 1918, 69622 Villeurbanne cedex (France), Fax: (+33) 472-44-6264 http://www.icbms.fr/casyen/45-casyen-andrioletti/23-andrioletti.
authors.forename: Ludivine
authors.initials: L
authors.lastname: Jean-Gérard
authors.affiliation: Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS-UMR CNRS 5246), Université Claude Bernard Lyon 1, Bâtiment Curien (CPE) 43, Bd du 11 Novembre 1918, 69622 Villeurbanne cedex (France), Fax: (+33) 472-44-6264 http://www.icbms.fr/casyen/45-casyen-andrioletti/23-andrioletti.
authors.forename: Eric
authors.initials: E
authors.lastname: Framery
authors.affiliation: Laboratoire des Multimatériaux et Interfaces (UMR 5615), Université Claude Bernard Lyon 1, 43, Bd du 11 Novembre 1918, 69622 Villeurbanne cedex (France).
authors.forename: Guillaume
authors.initials: G
authors.lastname: Pilet
authors.affiliation: Laboratoire de Chimie Quantique-UMR 7177, Institut de Chimie 1 rue Blaise Pascal 67081 Strasbourg (France).
authors.forename: Vincent
authors.initials: V
authors.lastname: Robert
authors.affiliation: Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS-UMR CNRS 5246), Université Claude Bernard Lyon 1, Bâtiment Curien (CPE) 43, Bd du 11 Novembre 1918, 69622 Villeurbanne cedex (France), Fax: (+33) 472-44-6264 http://www.icbms.fr/casyen/45-casyen-andrioletti/23-andrioletti. bruno.andrioletti@univ-lyon1.fr.
authors.forename: Bruno
authors.initials: B
authors.lastname: Andrioletti
keywords: asymmetric synthesis; chiral auxiliaries; computational studies; phosphanes; stereochemistry