decarbamoyl

Decarbamoylation is the chemical process of removing a carbamoyl group from a molecule. The term is used in organic chemistry and related fields to describe the loss of a carbamoyl protecting group or the hydrolysis of carbamate moieties, resulting in the regeneration of the underlying functional group, typically an amine, along with small inorganic or organic byproducts such as carbon dioxide or alcohols.

In practical terms, decarbamoylation often refers to deprotection reactions in which amines protected as carbamates are converted back to the free amine. Common carbamoyl protecting groups include Boc (tert-butyloxycarbonyl), Cbz (benzyloxycarbonyl), and Alloc (allyloxycarbonyl). Boc deprotection is typically accomplished under acidic conditions (for example with trifluoroacetic acid or hydrochloric acid), which releases carbon dioxide and a volatile byproduct and yields the free amine, usually as a salt. Cbz and Alloc groups can be removed by different strategies, such as catalytic hydrogenation or palladium-catalyzed methods, respectively, liberating the amine and small byproducts derived from the protecting groups. Hydrolytic decarbamoylation is another pathway, where carbamate groups are cleaved by acid or base to give the corresponding amine (or its salt) and carbon dioxide or an alcohol.

Decarbamoylation is widely used in organic synthesis and peptide chemistry to unveil amines after protective chemistry or to convert carbamate intermediates into reactive amines. The choice of method depends on the specific carbamoyl group, the substrate, and the desired reaction conditions, balancing selectivity, compatibility, and practicality.