Metal-Ligand Cooperation in the Catalytic Dehydrogenative Coupling (DHC) of Polyalcohols to Carboxylic Acid Derivatives

Several polyols, which are easily available from sugars through biochemical conversion or hydrogenolytic cleavage, are directly converted into carboxylic acids and amides. This efficient dehydrogenative coupling process, catalyzed by a rhodium(I) diolefin amido complex, is an attractive approach for the production of organic fine chemicals from renewable resources. This method tolerates the presence of several hydroxy groups and can be extended to the direct synthesis of lactams from the corresponding amino alcohols under mild conditions. Rhodium‐amide synergy for biomass conversion: The application of a rhodium(I) diolefin amido complex as an efficient catalyst for the selective dehydrogenative coupling (DHC) of polyols derived from renewable feedstocks with amines and water to the corresponding carboxylic acid derivatives is demonstrated. The direct access to medium‐sized‐ring lactams from amino alcohols, commonly embedded in the skeletons of bioactive natural products is also achieved.