A phosphoryl to spiro-bicyclophosphorane transformation via beta-amidic proton elimination in phosphorylated hydrazides

作者：Gholivand Khodayar^*; Mahzouni Hamid R; Molaei Foroogh; Kalateh Ali A

来源：Tetrahedron Letters, 2012, 53(44): 5944-5947.

DOI：10.1016/j.tetlet.2012.08.105

• (2)J(PH) Coupling constant
• Hydrazide
• Phosphoryl
• Spiro-bicyclophosphorane

The reaction between phosphoryl-containing reagents and hydrazides has been studied. The tetrahedral phosphoryl structure is transformed into a spiro-bicyclophosphorane system with trigonal bipyramidal geometry by the elimination of a beta-amidic proton in the reaction between a hydrazide and phosphoryl reagents with at least two leaving groups (Cl) bound to the phosphorus atom, such as POCl3 or PhPOCl2. In the spiro-bicyclophosphorane structure, the C=N imine bond is formed upon beta-amidic proton elimination, leading to the conversion of the C=O into a C-O bond and the formation of a P-O bond. All of these structural rearrangements are supported by X-ray crystallography data, and NMR and IR experiments.

• 出版日期2012-10-31