Institut de Chimie Moléculaire et des Matériaux d'Orsay

Laboratoire de Synthèse Organique et Méthodologie - LSOM

Nicolas Rabasso


Maître de Conférences
LSOM - ICMMO - Bât 420
Université Paris-Sud 11
15, rue Georges Clemenceau
91405 Orsay Cedex
FRANCE

Tel: +33 1 69 15 32 39 (office)
Tel: +33 1 69 15 72 52 (lab)
Fax: +33 1 69 15 62 78
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Aminophosphonates

Our research is focused on the synthesis of aminophosphonates intermediates with high regio- and stereocontrol. Indeed, phosphonate moiety is a key element in synthetic organic chemistry and associated with an amine it represents an emerging pharmacophore. Despite their wide use as herbicides, insecticides and fungicides, aminophosphonates plays an important role in human life and are used as HIV inhibitors, antitumor agents or antibiotics.

Our work is divided in three parts:

  1. Aminophosphonates Synthesis: Highly functionalized β-amino vinylphosphonates have been prepared from ynamides by a nickel(II)-catalyzed hydrophosphonylation reaction. The adducts are obtanied with high regio and stereoselectivity. Investigations on the mechanism of the reaction is under way to dertermine the scope and limitation of this transformation. (Collaboration Dr. G. Evano, Université de Versailles).


    In the course of our studies on the reactivity of ynamides with organophosphorus reagents, we recently reported a straightforward synthesis of α-amino allenephosphonates.

    » Related papers :
    "Highly Regio- and Stereoselective Nickel-Catalyzed Addition of Dialkyl Phosphites to Ynamides: an Efficient Synthesis of β-Aminovinylphosphonates" Fadel, A.; Legrand, F.; Evano, G.; Rabasso, N. Adv. Synth. Catal. 2011, 353, 263-267 [PDF]
    " [2,3]-Sigmatropic Rearrangement of Ynamides: Preparation of α-Amino Allenephosphonates " Gomes, F.; Fadel, A.; Rabasso, N. J. Org. Chem. 2012, 77, 5439-5444 [PDF]
     
  2. Preparation of Aminomethyl Vinylphosphonates: As part of our research on the reactivity of vinylphosphonates we have studied the synthesis of aminomethyl vinylphosphonates. These compounds are excellent partners for cycloaddition and 1,3-dipolar cycloaddition in particular.


    » Related paper: "Synthesis of new β- and γ-aminopyrrolidinephosphonates via 1,3-dipolar cycloaddition of substituted vinylphosphonates" Rabasso, N.; Fadel, A. Tetrahedron Lett. 2010, 51, 60-63 [PDF]
     
  3. Phosphonopeptide Synthesis: Since aminophosphonates are isosteres of aminoacids they represents the ideal condidats to modify and enhance the properties of peptides. Recently we have prepared an analogue of Met-enkephalin by replacement of methionine with our cyclic aminophosphonates.

    » Related paper: "Synthesis of an enkephalin analogue containing an α,α-disubstituted heterocyclic aminophosphonic acid" Rabasso N.; Fadel, A. Phosphorus, Sulfur Silicon Relat. Elem. 2011, 186, 1811-1819 [PDF].