HighlySelective Radical Relay 1,4-Oxyimination of Two Electronically Differentiated Olefins

Radical addition reactions of olefins have emerged as an attractive tool for the rapid assembly of complex structures, and have plentiful applications in organic synthesis, however, such reactions are often limited to polymerization or 1,2-difunctionaliza-tion. Herein, we disclose an unprecedented radical relay 1,4-oxyimination of two electronically differentiated olefins with a class of bifunctional oxime carbonate reagents via an energy transfer strategy. The protocol is highly chemo-and regioselective, and three different chemical bonds (C-O, C-C, and C-N bonds) were formed in a single operation in an orchestrated manner. Notably, this reaction provides rapid access to a large variety of structurally diverse 1,4-oxyimination products, and the obtained products could be easily converted into valuable biologically relevant delta-hydroxyl-alpha-amino acids. With a combination of experimental and theoretical methods, the mechanism for this 1,4-oxyimination reaction has been investigated. Theoretical calculations reveal that a radical chain mechanism might operate in the reaction.

Automated summary

Radical addition reactions of olefins are widely used in organic synthesis, but mainly limited to polymerization or 1,2-difunctionalization. This study presents an unprecedented radical relay 1,4-oxyimination of two electronically differentiated olefins using a class of bifunctional oxime carbonate reagents through an energy transfer strategy. The reaction is highly selective and diverse, providing rapid access to valuable products.