Reversing the Regioselectivity of Halofunctionalization Reactions through Cooperative Photoredox and Copper Catalysis.

Halofunctionalization of alkenes is a classical method for olefin difunctionalization. It gives rise to adducts which are found in many natural products and biologically active molecules, and offers a synthetic handle for further manipulation. Classically, this reaction is performed with an electrophilic halogen source and leads to regioselective formation of the halofunctionalized adducts.

Synthesis of α-Benzyloxyamino-γ-butyrolactones via a Polar Radical Crossover Cycloaddition Reaction.

A direct catalytic synthesis of substituted α-benzyloxyamino-γ-butyrolactones is reported, starting from simple oxime acids and alkenes. The substituted O-benzyloxime acid starting materials are cyclized with oxidizable alkenes, via Polar Radical Crossover Cycloaddition (PRCC) reactions. The catalytic reaction is carried out using the Fukuzumi acridinium photooxidant and substoichiometric amounts of a redox-active cocatalyst.