Ackerman LK. G,
Alvarado JI. M,
Doyle AG.
* Princeton University, USA
Direct C–C Bond Formation from Alkanes Using Ni-Photoredox Catalysis.
J. Am. Chem. Soc. 2018;
140: 14059-14063
Key words
nickel catalysis - photoredox catalysis - C–H functionalization
Significance
The authors developed a nickel-photoredox-catalyzed C(sp3)–H functionalization of a variety of unactivated alkyl or benzyl compounds using chloroformate derivatives. Mild coupling conditions allow the tolerance of several functional groups, leading to the corresponding carbonyl compounds in good yields.
Comment
From a mechanistic point of view, the authors hypothesized a catalytic cycle, which starts with an oxidative addition of chloroformate to a nickel(0) species. A SET forms a nickel(III) intermediate, which undergoes subsequent photoelimination, leading to a chlorine radical. Following H-abstraction results in a carbon-centered radical. Addition of the nickel(II) complex and subsequent reductive elimination affords the carbonyl compound.
