Photochemical C-H Activation Enables Nickel-Catalyzed Olefin Dicarbofunctionalization

Alkenes, ethers, and alcohols account for a significant percentage of bulk reagents available to the chemistry community. The petrochemical, pharmaceutical, and agrochemical industries each consume gigagrams of these materials as fuels and solvents each year. However, the utilization of such materials as building blocks for the construction of complex small molecules is limited by the necessity of prefunctionalization to achieve chemoselective reactivity. Herein, we report the implementation of efficient, sustainable, diaryl ketone hydrogen-atom transfer (HAT) catalysis to activate native C-H bonds for multicomponent dicarbofunctionalization of alkenes. The ability to forge new carbon-carbon bonds between reagents typically viewed as commodity solvents provides a new, more atom-economic outlook for organic synthesis. Through detailed experimental and computational investigation, the critical effect of hydrogen bonding on the reactivity of this transformation was uncovered.

Automated summary

Alkenes, ethers, and alcohols are commonly used bulk reagents in the chemistry community, serving as fuels and solvents in industries such as petrochemical, pharmaceutical, and agrochemical. However, their utilization as building blocks for complex small molecules is limited by the need for prefunctionalization to achieve high selectivity.