Stereocontrolled Radical-Recombination

  • Author: Li Grundl
  • Published: 06 December 2017
  • Copyright: Wiley-VCH Verlag GmbH & Co. KGaA
  • Source / Publisher: Journal of the American Chemical Society/ACS Publishing
  • Associated Societies: American Chemical Society (ACS), USA
thumbnail image: Stereocontrolled Radical-Recombination

Catalytic and asymmetric functionalization of C(sp3)–H is a sustainable method to construct stereogenic carbon centers. Although many methods have been well established for α-C(sp3)–H functionalization of carbonyl compounds, only limited studies are known for β-C(sp3)–H funcationalization.

Eric Meggers, Pilipps-Universität Marburg, Germany, and colleagues have developed a visible-light-activated asymmetric β-C–H functionalization of 2-acyl imidazoles and 2-acylpyridines with 1,2-dicarbonyl compounds. A stereogenic-at-rhodium Lewis acid has been used as a catalyst to give the products in high yields with excellent stereoselectivities. The experiments are carried out in the presence of catalytic amount of DABCO (1,4-diazabicyclo[2.2.2]octane) under blue LED radiation in acetone at room temperature.

According to experimental and computational studies, the researchers proposed a mechanism in which an electron-rich Rh-enolate radical and an α-hydroxyl radical are formed and a stereocontrolled radical-radical recombination occur (pictured). They also found that the reaction strongly depended on the structure of the carbonyl compounds.


 

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