Download PDF
Synlett 1998; 1998(1): 73-75
DOI: 10.1055/s-1998-1560
letter
© Georg Thieme Verlag, Rüdigerstr. 14, 70469 Stuttgart, Germany. All rights reserved. This journal, including all individual contributions and illustrations published therein, is legally protected by copyright for the duration of the copyright period. Any use, exploitation or commercialization outside the narrow limits set by copyright legislation, without the publisher's consent, is illegal and liable to criminal prosecution. This applies in particular to photostat reproduction, copying, cyclostyling, mimeographing or duplication of any kind, translating, preparation of microfilms, and electronic data processing and storage.

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
Further Information

Publication History

Publication Date:
31 December 2000 (online)

  PDF Download  Permissions and Reprints All articles of this category

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

      >