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Synlett 1998; 1998(1): 73-75
DOI: 10.1055/s-1998-1560
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New Highly Diastereoselective Synthesis of Phosphoramidates. A Route to Chiral Methyl p-Nitrophenyl Alkylphosphonates

Jean-François Cavalier* , Frédéric Fotiadu, Robert Verger, Gérard Buono
  • *ENSSPICAM, UMR 6516, Synthèse, Catalyse et Chiralité, Avenue Escadrille Normandie-Niemen, F-13397 Marseille Cedex 20; Fax (+33) 4 91 0 27 7 76; E-mail: buono@spi-chim.u-3mrs.fr
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Publication Date:
31 December 2000 (online)

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A new, efficient and highly enantioselective synthesis of methyl p-nitrophenyl alkylphosphonates 4 a-c is described. Alkylphosphonic dichloride 1 a-d reacted successively with L-proline ethyl ester and p-nitrophenol to afford phosphoramidates 3 a-d in 97% de. Boron trifluoride catalysed methanolysis gave 4 a-c with 93% ee. Absolute configurations of compounds 4 c and 3 c were established by correlation with the X-ray structure of HPL-colipase-(-)-4 c complex. 31P NMR studies indicates that monochloro phosphoramidates (R p )- and (S p)-2 c undergo fast epimerisation. The observed diastereoselectivity in favour of (S p)-3 c results from a faster reaction of (R p)-2 c as compared to its epimer, according to the Curtin-Hammett principle.

asymmetric synthesis - alkylphosphonates - enantioselectivity - L-proline derivatives