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We have studied a variety of nucleophilic displacements including those using sodium azide, sodium thiocyanate, imidazole, triethyl phosphite, and thiazolidinecarboxylic acid. DMF seems to be the solvent of choice on the basis of reagent solubility, anion nucleophilicity, and effective monolayer surface wetting. There is some evidence that increasing the water content of the DMF can reduce its ability to wet the substrate surface and thereby slow down the desired nucleophilic displacement.
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note
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We gratefully acknowledge the assistance of Dr. Connie Johns, now of Shaman Pharmaceutical, for the acquisition of this XPS spectrum.
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53
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note
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H2 reaction with solution phase ditin species by the intermediate monolayer-bound alkyl radical. Both the substantial steric effect of neighboring trimethyltin substituents and the solution phase concentrations favor hydrogen atom abstraction over homolytic stannylation.
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The solvents tested included acetonitrile, nitromethane, cyclohexane, THF, diethyl ether, acetone, DMF, toluene, triethylamine, pyridine, dichloromethane, and chloroform.
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Fryxell, G. E.; Linehan, J. C.; Rieke, P. C.; Coffey, G. To be reported separately
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It has been reported that these esters were partially hydrolyzed by treatment with concentrated hydrochloric acid, but we had difficulty reproducing this (see ref 59).
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