thiolýza
Thiolýza is the chemical process by which a bond is broken under the action of a thiol (R–SH) or its conjugate base, a thiolate (RS−). In organic chemistry, thiolýza refers to nucleophilic substitution or exchange reactions in which a thiolate attacks a substrate to cleave a bond and form a new thioester or thioether. Common substrates include thioesters, esters, and acyl halides, where thiols promote cleavage or exchange of the acyl group. A typical outcome is the formation of a new thioester or the release of an alcohol or halide, depending on the substrate and conditions. Thiolýza is a key step in trans-thioesterification processes such as native chemical ligation in peptide synthesis, where a cysteine-containing peptide reacts with a peptide thioester to form a longer polypeptide, followed by an acyl shift to yield a native amide bond.
In biochemistry, thiolýza often refers to thiol-disulfide exchange and the reduction of disulfide bonds. Thiol-containing molecules
Related topics include disulfide reduction, thiol-disulfide exchange, and native chemical ligation.