2-naphthalenesulfonyl as a tosyl substitute for protection of amino functions. Cyclic voltammetry studies on model sulfonamides and their preparativecleavage by reduction

With the aim to develop a practically useful, reductively more labile alter native to tosyl for protection of amino functions, initially a number of N- arenesulfonyl-protected heterocycles (pyrroles, imidazoles, indole, and car bazole) have been prepared and studied by cyclic voltammetry (CV). The reco rded activation potentials vary from -1.32 to -1.99 V (vs SCE). In N-sulfon ylazolides such as tosylindole the cathodic potentials are shifted by over 0.5 V compared to simple sulfonamides. An additional effect of the sulfonic acid component is also indicated. Among the compounds studied, 1- and 2-na phthalenesulfollylindole give CV peaks at about 0.4 and 0.2 V, respectively , less negative potential than tosylindole. To further investigate naphthal enesulfonyl for this purpose, we have also prepared a variety of simple 1- and 2-naphthalenesulfonyl derivatives and studied them similarly. They have activation potentials above -2.14 V and are all smoothly cleaved by Mg/MeO H. The latter reagent is capable of cleaving N-arenesulfonyl derivatives th at give CV peaks above -2.30 V, whereas Al(Hg) requires potentials above ab out -1.7 V. Selective cleavage of 2-naphthalenesulfonyl in the presence of tosyl by Mg/MeOH is demonstrated. Several examples of reductive cleavage of arenesulfonyl derivatives with Mg/MeOH, Al(Hg), and electrolysis on a prep arative scale are given.