On the Absolute Configurational Stability of Bromonium and Chloronium Ions

Halonium ions have long been established as the critical intermediates in halogenation and halo functionalization of alkenes. Although these workhorse reactions have been extensively studied mechanistically and employed synthetically, the paucity of enantioselective variants is striking. A central problem in the development of catalytic enantioselective halofunctionalizations is the reversible formation of halonium ions and the facile olefin-to-olefin transfer. In this report, configurationally defined and enantiomerically enriched bromonium and chloronium ions are generated (by solvolysis of enantiomerically enriched precursors) and shown to be intercepted intermolecularly with high enantio- and diastereospecificity by various nucleophiles. Most importantly, the stereospecificity of capture is not significantly eroded in the presence of olefins.