Laboratoire de Synthèse Organique et Méthodologie, ICMMO, UMR CNRS 8182, Bât. 420, Université Paris-Sud, 15 rue Georges Clemenceau, 91405 Orsay Cedex, France.
J Org Chem. 2012 Jun 15;77(12):5439-44. doi: 10.1021/jo300790m. Epub 2012 May 30.
α-Amino allenephosphonates were easily prepared in two steps from protected amines, propargyl alcohols, and chlorophosphites. First, ynamides were synthesized from unprotected 1-bromopropargyl alcohols using a copper(II) catalyzed coupling reaction. In the second step, the previously prepared ynamides were transformed directly to allenes through a [2,3]-sigmatropic rearrangement of propargyl phosphites. This efficient method led to the formation of a series of α-amino allenephosphonates with diverse substituents on the amine, the phosphonate, and the allene moieties.
α-氨基酸烯基膦酸酯可以通过两步反应，从保护的胺、炔丙醇和亚膦酸氯盐很容易地制备得到。首先，使用铜(II)催化的偶联反应，从非保护的 1-溴丙炔醇合成了炔酰胺。在第二步中，以前制备的炔酰胺通过炔丙基膦酸酯的[2,3]-σ重排直接转化为烯丙基化合物。这种有效的方法导致了一系列具有不同取代基的α-氨基酸烯基膦酸酯的形成，包括胺、膦酸酯和烯丙基部分。
