Phosphonylation of Biomolecules with Inorganic Diphosphonate. II. Phosphonylation of Phosphate Groups on Nudeoside 5′-Monophosphates, Deoxynudeoside 5′-Monophosphates, and Sugar Phosphates

Abstract

Inorganic diphosphonate phosphonylated predominantly phosphate groups on nucleoside 5′-monophosphates (=NMP’s: AMP, GMP, IMP, CMP, and UMP), deoxynudeoside 5′-monophosphates (=dNMP’s: dAMP and dTMP), and sugar phosphates (=SP’s: GlclP, Glc6P, and Rib5P) in aqueous solutions under mild conditions (50–70 °C, pH 6). The chemical structures of phosphonylated products were discussed on their 31P NMR spectra and high-performance liquid chromatograms. The main phosphonylated products from NMP’s and dNMP’s were analogous in structure to nucleoside 5′-diphosphates. The rate of phosphonylation of phosphate groups on NMP’s, dNMP’s, and SP’s varied strongly depending on reaction conditions: pH, reaction temperature, and initial concentration of inorganic diphosphonate. The maximum yields of phosphonylated products were ca. 70% for all NMP’s, dNMP’s, and SP’s under the following conditions: initial concentration of inorganic diphosphonate is 1.5 mol dm−3; each initial concentration of NMP’s, dNMP’s, or SP’s is 0.1 mol dm−3; 70 °C; pH 6.

Phosphonylation of L-Dopa With Sodium Diphosphonate in Aqueous Solution

“…One of the authors reported the phosphonylation of nucleoside 5'-monophosphate 7 and nucleoside 5'-diphosphate 8 by DP. According to Scheme 1, the phosphonyl transfer reaction was performed at 5'-monophosphate of the β-D-ribofuranosyl unit to form an H-phosphonate analogue of 5'-ADP.…”

“…A previous work indicated that the phosphonylation product of adenosine 5'-monophosphate 7 with DP is H-phosphonate esters with a P-H bond.…”

Phosphonylation of 5’-Deoxy-5-Fluorouridine and 1-?-D-Arabinofuranosylcytosine With Disodium Diphosphonate

“…Yamamoto et al previously studied that adenosine 5'-monophosphate was phosphonylated by DP to give an analogue of adenosine 5'-diphosphate (5'-ADP) 11 . Later, they have reported the phosphonylation of nucleoside 5'-diphosphate with DP in order to form H-phosphonate analogues of nucleotide 5'-triphosphate (5'-NTP) 12 .…”

Introduction of Phosphonate Group Into Kojic Acid by Diphosphonate

“…Because of its unique structure, biologically important compounds having a hydroxyl group can be phosphonylated by DP. Baba et al reported the phosphonylation of nucleoside 5'-monophosphate 12 and nucleoside 5'-diphosphate 13 with DP to form H-phosphonate analogues of 5'-ADP and 5'-ATP. More recently, our group studied the phosphonylation of salicin with DP 14 .…”