Experimental and Theoretical Investigations of the Stereoselective Synthesis of P‐Stereogenic Phosphine Oxides |
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| Authors: | Laurent Copey Dr. Ludivine Jean‐Gérard Dr. Eric Framery Dr. Guillaume Pilet Prof. Vincent Robert Prof. Bruno Andrioletti |
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| Affiliation: | 1. Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS‐UMR CNRS 5246), Université Claude Bernard Lyon 1, Batiment 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;2. Laboratoire des Multimatériaux et Interfaces (UMR 5615), Université Claude Bernard Lyon 1, 43, Bd du 11 Novembre 1918, 69622 Villeurbanne cedex (France);3. Laboratoire de Chimie Quantique—UMR 7177, Institut de Chimie 1 rue Blaise Pascal 67081 Strasbourg (France) |
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| 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 PV 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 PIII phosphine precursor afforded a P‐epimer oxazaphospholidine. Hence, the two enantiomeric phosphine oxides can be synthesized starting from either a PV or a PIII phosphine precursor, which constitutes a clear advantage for the stereoselective synthesis of sterically hindered phosphine oxides. |
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| Keywords: | asymmetric synthesis chiral auxiliaries computational studies phosphanes stereochemistry |
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