Preparation of Phosphostatine Analogues From L-amino acids

Ricardo de la Cruz-Cordero, Victoria Labastida-Galván, Mario Fernández-Zertuche, and Mario Ordóñez*

Centro de Investigaciones Químicas. Universidad Autónoma del Estado de Morelos. Av. Universidad 1001. Cuernavaca 62210, Morelos, México. E-mail: palacios@ciq.uaem.mx

Recibido el 4 de julio del 2005. ]]> Aceptado el 18 de octubre del 2005.

Abstract

Reduction of (3S)-N,N-dibenzylamino-2-ketophosphonates 9a-d derived from L-amino acids was carried out with catecholborane at -20 ^oC to afford the (3S)-N,N-dibenzylammo-(2R)-hydroxy-phosphonates syn-10a-d, whereas the reduction of (3S)-N-benzylamino-2-ketophosphonates 13a-d with Zn(BH₄)₂ at -78 ^oC yield (3S)-N-benzylamino-(2S)-hydroxyphosphonates anti-14a-d. The reduction in both cases was in good chemical yields and with high diastereoselectivity. The hydrolysis and hydrogenolysis of 10a-d and 14a-d afford the (3S)-amino-(2R)-hydroxyphosphonic acids 6 and (3S)-amino-(2S)-hydroxyphosphonic acids 7, respectively, which are analogues of phosphostatine.

Keywords: Phosphostatine, aminophosphonic acids, β-ketophosphonates, diastereoselective reduction.

Resumen

La reducción de (3S)-N,N-dibencilamino-2-cetofosfonatos 9a-d preparados a partir de L-aminoácidos se llevó a cabo con catecolborano a -20 ^oC, obteniendo los (3S)-N,N-dibencilamino-(2R)-hidroxifosfonatos syn-10a-d, mientras que la reducción de los (3S)-N-bencilamino-2-cetofosfonatos 13a-d con Zn(BH₄)₂ a -78 ^oC produce los (3S)-N-bencilamino-(2S)-hidroxifosfonatos anti-14a-d. La reducción en ambos casos procede con buen rendimiento químico y con una alta diastereoselectvidad. La hidrólisis e hidrógenolisis de los hidroxifosfonatos 10a-d y 14a-d proporciona a los ácidos (3S)-amino-(2R)-hidroxi-fosfónicos 6 y (3S)-amino-(2S)-hidroxifosfónicos 7, respectivamente, los cuales son análogos de la fosfoestatina.

Palabras clave: Fosfoestatina, ácidos aminofosfónicos, β-cetofosfonatos, reducción diasteroselectiva.

Acknowledgments

We wish to thank CONACYT of Mexico, for financial support via grant 41657-Q for this work, and to Citlali Quiñónes and Emanuel Hernández for technical support. One of us, RCC, also wishes to thank CONACYT for a Graduate Scholarship.

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