Journal
INORGANIC CHEMISTRY
Volume 51, Issue 1, Pages 328-335Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic2016897
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Funding
- NSF-RUI [CHE-0956740]
- Lewis & Clark College John S. Rogers Science Foundation
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [0956740] Funding Source: National Science Foundation
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The utility of phosphonothioate methanolysis to degrade organophosphate neurotoxins has prompted the stereochemical investigation of this useful transformation. The methanolysis of enantiomerically pure O,S-diethyl phenylphosphonothioate (5) was studied both in the presence and in the absence of metal ions known to catalyze the phosphonothioate -> phosphonate transformation. This report outlines the syntheses of enantiomerically pure 5 and its methanolysis product O-ethyl O-methyl phenylphosphonate (7). Compound 7 results from exclusive P-S scission of 5, which is the desired mode of phosphonothioate methanolysis (E-a = 14.5 +/- 0.5 kcal/mol). The stereochemical analysis of the phosphonothioate methanolysis was done for the first time with beta-cyclodextrin, and it shows complete inversion on the phosphorus center upon methoxide displacement of ethanethiolate. The presence of La(III) or Zn(II) complexes do not alter this S(N)2-like substitution which sheds new light on the mechanism of methanolysis of phosphonothioates.
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