Nitrous Oxide as a Hydrogen Acceptor for the Dehydrogenative Coupling of Alcohols

Abstract

Abstract The oxidation of alcohols with N 2 O as the hydrogen acceptor was achieved with low catalyst loadings of a rhodium complex that features a cooperative bis(olefin)amido ligand under mild conditions. Two different methods enable the formation of either the corresponding carboxylic acid or the ester. N 2 and water are the only by‐products. Mechanistic studies supported by DFT calculations suggest that the oxygen atom of N 2 O is transferred to the metal center by insertion into the Rh−H bond of a rhodium amino hydride species, generating a rhodium hydroxy complex as a key intermediate.