ChemInform Abstract: Addition Reactions of Tris(trimethylsilyl)germyl Radicals to Unsaturated Compounds. An EPR and Product Study.

Abstract

Addition Reactions of Tris(trimethylsilyl)germyl Radicals to Unsaturated Compounds. An EPR and Product Study.-The preparative scale reactions of the germyl radical, generated from hydride (II), with a variety of alkenes and alkynes are studied. With alkenes like vinylcyclohexane, vinyltrimethylsilane, and 2,3-dihydrofuran no addition products are observed. Only pyridine (I) reacts with the radical yielding product (III), probably because of a resonance stabilized intermediate adduct, longliving enough to undergo subsequent hydrogen transfer from the germane. The reaction with alkynes (IV) proceeds regio-and stereoselectively with exclusive formation of (Z)-2-alkenylgermanes (V). EPR studies are made with the radical and arylalkenes, ketones, quinones, azines, and nitroalkanes. In most cases the corresponding adducts are detected, with azines no adducts are obtained. -(BERNARDONI, S.; LUCARINI, M.; PEDULLI, G. F.; VALGIMIGLI, L.; GEVORGYAN, V.; CHATGILIALOGLU, C.; J.