Scientific publications
Other affiliations: University of Minho
Leif Grehn
Other affiliations: University of Minho
Hernâni L. S. Maia
Other affiliations: University of Minho
Luı́s S. Monteiro
Other affiliations: University of Minho
Ulf Ragnarsson
Other affiliations: University of Minho
The Journal of Organic Chemistry
With the aim to develop a practically useful, reductively more labile alternative to tosyl for protection of amino functions, initially a number of N -arenesulfonyl-protected heterocycles (pyrroles, imidazoles, indole, and carbazole) have been prepared and studied by cyclic voltammetry (CV). The recorded activation potentials vary from −1.32 to −1.99 V (vs SCE). In N -sulfonylazolides 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-naphthalenesulfonylindole give CV peaks at about 0.4 and 0.2 V, respectively, less negative potential than tosylindole. To further investigate naphthalenesulfonyl 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/MeOH. The latter reagent is capable of cleaving N -arenesulfonyl derivatives that give CV peaks above −2.30 V, whereas Al(Hg) requires potentials above about −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 preparative scale are given.
