Nitrous oxide (N₂O) is a potent greenhouse gas, but can also be useful, e.g., in medicine or as an oxygen transfer reagent in chemistry. When used as an oxygen transfer reagent, it releases non-toxic nitrogen. However, it can be challenging to activate N₂O using transition-metal catalysts for use in organic synthesis.

Josep Cornella, Max Planck Institute for Coal Research, Mülheim an der Ruhr, Germany, and colleagues have developed a protocol for the catalytic synthesis of cycloalkanols (pictured, X = O, CH₂), using N₂O as an oxygen transfer agent. The team used NiI₂ as a catalyst together with a phenanthroline-based ligand to convert alkene-substituted aryl iodides to the corresponding cycloalkanols in the presence of NaI and activated zinc. The reactions were performed in dimethyl sulfoxide (DMSO) as the solvent under 2.5 atm of N₂O at 25 °C.

The desired products were obtained in generally moderate to high yields. The researchers also tested the same protocol with a chiral, imidazolylpyridine-based ligand. They found that the reaction can be performed in an enantioselective manner with high enantioselectivities when such chiral ligands are used. Mechanistic studies indicate that N₂O is the oxygen transfer reagent in this protocol. This could also be useful for the synthesis of other oxygenated compounds in organic synthesis.

• Ni-Catalyzed Oxygen Transfer from N₂O onto sp³-Hybridized Carbons,
  Shengyang Ni, Franck Le Vaillant, Ana Mateos-Calbet, Ruben Martin, Josep Cornella,
  J. Am. Chem. Soc. 2022.
  https://doi.org/10.1021/jacs.2c06227