Pancratistatin cyclic phosphate prodrugs and phenpanstatin...

Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Phosphorus containing other than solely as part of an...

Reexamination Certificate

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C514S280000, C514S287000

Reexamination Certificate

active

07541346

ABSTRACT:
Selective phosphorylation of phenpanstatin (3a) with tetrabutylammonium dihydrogen phosphate and dicyclohexylcarbodiimide in pyridine followed by cation exchange chromatographic procedures was found to provide an efficient route to a new series (3b-3d) of promising 3,4-O-cyclic phosphate prodrugs designated phenpanstatin phosphates. Application of analogous reaction conditions to pancratistatin (1a) led to a mixture of monophosphate derivatives where sodium pancratistatin 4-O-phosphate (4a) was isolated and the structure confirmed by x-ray crystallography. Modification of the reaction conditions allowed direct phosphorylation of pancratistatin followed by cation exchange chromatography to afford sodium pancratistatin 3,4-O-cyclic phosphate (5b) which was selected for preclinical development.

REFERENCES:
patent: 7351830 (2008-04-01), Pettit et al.
patent: WO 02/50023 (2002-06-01), None
Pettit, G.R. et al.: Antineoplastic agents 500. Narcistatin. J. Nat. Prod., vol. 66, pp. 92-96, 2003.
International Search Report for PCT/US04/19725 dated Jan. 11, 2005.
Written Opinion of the International Search Authority for PCT/US04/19725 dated Jan. 11, 2005.
Pettit et al., “Antineoplastic Agents. 511. Direct Phosphorylation of Phenpanstatin and Pancratistatin”,J. Nat. Prod., 67:322-327, (2004).
Mamber et al., “Tubulin Polymerization by Paclitaxel (Taxol) Phosphate Prodrugs After Metabolic Activation with Alkaline Phosphatase”,The Journal of Pharmacology and Experimental Therapeutics, 274(2):877-883 (1995).
Shnyder et al., “Sodium Pancratistatin 3,4-O-Cyclic Phosphate, a Water-Soluble Synthetic Derivative of Pancratistatin, is Highly Effective in a Human Colon Tumor Model”,J. Nat. Prod., 71:321-324 (2008).

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