Formation of Diphosphates. A NMR Study on the Mechanism and Stereochemistry of Diphosphate Formation from Chiral Dioxaphosphorinanes

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• 作者：Ron Hulst ; Johanna M. Visser ; N. Koen de Vries ; Robert W. J. Zijlstra ; Huub Kooijman ; Wilberth Smeets ; Anthony L. Spek ; and Ben L. Feringa
• 刊名：Journal of the American Chemical Society
• 出版年：2000
• 出版时间：April 5, 2000
• 年：2000
• 卷：122
• 期：13
• 页码：3135 - 3150
• 全文大小：242K
• 年卷期：v.122,no.13(April 5, 2000)
• ISSN：1520-5126

文摘

During the use of chiral 2-oxo-1,3,2-dioxaphosphorinanes as derivatizing reagents in the enantiomericexcess determination of amines, alcohols, and unprotected amino acids, minor traces of side reaction productswere observed by ¹H and ³¹P NMR spectroscopy. Analysis of the reaction mixture showed that the side productsare in fact diphosphates and several intermediates leading to their formation. From an analytical, mechanistic,and stereochemical point of view, the study of unexpected new reaction intermediates leading to diphosphatesis of particular interest. Due to the easy structural modification of the starting materials in both enantiomericallypure and racemic forms as well as easy access to oxygen-labeled materials for complete structural elucidationof both intermediates and diphosphates, we accomplished a complete structural analysis. Also a mechanisticproposal for their formation proved possible using 1D and 2D ¹H and ³¹P NMR techniques as well as theX-ray data of both starting material and two of the products.