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2-Naphthalenesulfonyl as a Tosyl Substitute for Protection of Amino Functions. Cyclic Voltammetry Studies on Model Sulfonamides and Their Preparative Cleavage by Reduction

1999; American Chemical Society; Volume: 64; Issue: 19 Linguagem: Inglês

10.1021/jo990695q

1520-6904

Barthélemy Nyasse, Leif Grehn, Hernâni L. S. Maia, Luı́s S. Monteiro, Ulf Ragnarsson,

Chemical Synthesis and Reactions

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.