2,4-Dinitrophenol as an activating reagent in a facile preparation of cyclic phosphate triesters

• Published in: Tetrahedron letters Vol. 45; no. 5; pp. 1001 - 1004
• Main Authors: Amigues, Eric J., Migaud, Marie E.
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 26-01-2004
• Subjects: Carbohydrate; Cyclic phosphate; Cyclic phosphite; Phosphoramidite; Carbohydrate; Phosphoramidite; Cyclic phosphite; Cyclic phosphate
• ISSN: 0040-4039; 1873-3581
• DOI: 10.1016/j.tetlet.2003.11.101

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2,4-Dinitrophenol was employed with benzyloxy-bis-(diisopropylamino)phosphine to synthesise the cyclic phosphate derivatives of a series of alkane diols (HO–(CH
2)
n
–OH,
n=2–6) in good isolated yields. Tetrazole and DNP were compared by
31P NMR spectroscopy for their ability to catalyse the cyclisation at the P(III) stage. Investigation of the phosphate triester stability under various oxidation and chromatographic conditions resulted in the optimisation of the isolation procedures of the chemically unstable cyclic compounds. Conditions for debenzylation were developed to yield the corresponding cyclic phosphodiesters quantitatively. The methodology was further applied to the preparation and isolation of the cyclic phosphate derivative of a carbohydrate.