Deprotection by electrolysis

The mechanism of the cathodic cleavage of tosylate protecting groups from alcohols, amines and phenols in dimethylformamide has been probed using the technique of homogeneous redox catalysis. Some nine tosyl esters and six tosyl amides have been investigated and it is confirmed that these deprotecti...

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Bibliographic Details
Published in:Journal of electroanalytical chemistry and interfacial electrochemistry 1984-04, Vol.164 (2), p.347-361
Main Authors: Maia, H.L.S., Medeiros, M.J., Montenegro, M.I., Court, D., Pletcher, D.
Format: Article
Language:English
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Summary:The mechanism of the cathodic cleavage of tosylate protecting groups from alcohols, amines and phenols in dimethylformamide has been probed using the technique of homogeneous redox catalysis. Some nine tosyl esters and six tosyl amides have been investigated and it is confirmed that these deprotection reactions occur by cleavage of the anion radicals. The formal electrode potentials for the couples, neutral molecule/anion radical, are reported and it is shown that the rate constants for the cleavage of the anion radicals lie in the range 10 4 s −1 to >10 8 s −1. Indeed for aromatic amines and phenols, the homogeneous charge transfer between the catalyst and the substrate becomes the rate determining step.
ISSN:0022-0728
DOI:10.1016/S0022-0728(84)80217-X