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Stability and Efficiency of Mixed Aryl Phosphonate Prodrugs
Journal article

Stability and Efficiency of Mixed Aryl Phosphonate Prodrugs

Benjamin J Foust, Jin Li, Chia‐Hung Christine Hsiao, David F Wiemer and Andrew J Wiemer
ChemMedChem, Vol.14(17), pp.1597-1603
09/04/2019
DOI: 10.1002/cmdc.201900344
PMCID: PMC6726502
PMID: 31226236

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Abstract

A set of phosphonate prodrugs of a butyrophilin ligand was synthesized and evaluated for plasma stability and cellular activity. The mixed aryl acyloxy esters were prepared either via a standard sequence through the phosphonic acid chloride, or through the more recently reported, and more facile, triflate activation. In the best of cases, this class of prodrugs shows cellular potency similar to that of bis‐acyloxyalkyl phosphonate prodrugs and plasma stability similar to that of aryl phosphonamidates. For example, {[((3E)‐5‐hydroxy‐4‐methylpent‐3‐en‐1‐yl) (naphthalen‐2‐yloxy)phosphoryl]oxy}methyl 2,2‐dimethylpropanoate can activate BTN3A1 in K562 cells after just 15 minutes of exposure (at an EC50 value of 31 nm) and is only partially metabolized (60 % remaining) after 20 hours in human plasma. Other related novel analogues showed similar potency/stability profiles. Therefore, mixed aryl acyloxyalkyl phosphonate prodrugs are an exciting new strategy for the delivery of phosphonate‐containing drugs. Speed and staying power: Quick‐acting bis‐acyloxyalkyl prodrugs are poorly stable in blood, whereas stable aryl‐phosphonamidates are slow to act. The novel aryl acyloxyalkyl prodrug 12 displays the best of both worlds: it acts quickly (15 min EC50=31 nm), but is also plasma stable (t1/2>20 h).
BTN3A1 butyrophilin phosphoantigens phosphorus prodrugs

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