Lewis Acid-Catalyzed Halonium Generation for Morpholine Synthesis and Claisen Rearrangement.

We disclose here practical strategies toward the synthesis of morpholines and Claisen rearrangement products based on the divergent reactivity of a common halonium intermediate. These reactions employ widely available alkenes in a Lewis acid-catalyzed halo-etherification process that can then transform them into the desired products with exceptional regioselectivity for both activated and unactivated olefins. Our mechanistic probe reveals an interesting regiochemical kinetic resolution process.

Halonium Catalysis: An Underutilized and Underexplored Catalytic Concept in Olefin Functionalizations.

Iodonium catalysis is described here to accomplish an intermolecular olefin oxyamination reaction. Urea is used as the O- and N-source to add across both activated and unactivated alkenes in a regioselective manner. Mechanistic studies confirm the presence of an iodonium intermediate.