The Synthesis And Atherton-Todd Reaction Study Of Valine Hymonspirophosphorane

Phosphorus plays an important role in prebiotic evolution and in process of the life, which is known as " the control center of the life activities ". Moreover, pentacoordinate phosphorus compounds as intermediates or transition-state species are essential in numerous biological processes. Hydrospirophosphorane(HSP) is a special type of pentacoordinate phosphoranes involving P-H bond, which is active enough to be precursors for organic synthesis. There are some preliminary explorations in synthesis and chemical properties of the Hymonspirophosphorane, which is synthesized from one molecular amino acid. However, up to now, their chemical activities of the Atherton-Todd reaction have not been reported in the literature. Therefore, in this paper, we first investigated the chemical activities of the Atherton-Todd reaction of Valine Hymonspirophosphorane.In the synthesis the Valine Hymonspirophosphorane, we explored five different kinds of Hymonspirophosphorane, and obtained two kinds of Valine Hymonspirophosphoranes. The reaction conditions were optimized, and good yields of the reactions in mild conditions were achieved. At the same time the stability and hydrolysis properties of Hymonspirophosphorane were also examined, and the results may lay a foundation to the synthesis of the new phosphorus compounds from Hymonspirophosphoranes.The effects of solvent, alkalis, amine dosage on the Atherton-Todd reaction of Valine Hymonspirophosphorane with primary amine were studied in detail. The possibilities of the Atherton-Todd reaction of Valine Hymonspirophosphorane with phenol-blocked, secondary amine and tertiary amine were also tested. It was found that the properties of Hymonspirophosphorane are far different from other Hydrospirophosphorane. A preliminary comparison between these two kinds of hydrospirophosphorane compounds will provide some help to synthesize new kinds of pentacoordinate phosphorane compounds. We totally synthesized6new pentacoordinate phosphorane compounds from ethylene glycol, and obtained,4new pentacoordinate phosphorane compounds from catechol. The structures of10novel spirophosphoranes were all identified by NMR, ESI-MS and IR.