Photoinduced nickel-catalyzed C(sp3)-C(sp2) cross-coupling via radical Brook rearrangement

Abstract

Ketyl radical is a type of useful radical intermediates to form alcohol compounds. Radical Brook rearrangement is one of the most important methods to generate ketyl radical. However, the application of ketyl radical formed by radical Brook rearrangement focused on direct nucleophilic attack or radical-radical coupling. It greatly limited the application of ketyl radical formed by radical Brook rearrangement. Therefore, this thesis mainly studies the trapping of ketyl radical formed by photoinduced radical Brook rearrangement using transition metal nickel and final formation of C(sp3)–C(sp2) cross-coupling product with aryl bromides. Besides, a reasonable mechanism merging photoinduced radical Brook rearrangement and nickel catalysis was proposed based on experimental results. In terms of practicality, this thesis provides new insights into the synthesis of high value-added and potentially bioactive alcohol compounds under mild and environmentally friendly conditions. In terms of fundamental theory, it also provides case basis for further research on merging photoinduced radical Brook rearrangement with other transition metals and forming product with other electrophiles and nucleophiles. I hope this article may inspire further development in research of radical Brook rearrangement.