Thioesters hydrolyze to thiols and the carboxylic acid:
:RC(O)SR'  +  HO  →  RCOH  +  RSH
The carbonyl center in thioesters is more reactive toward amine than oxygen nucleophiles, giving amides:
This reaction is exploited in native chemical ligation, a protocol for peptide synthesis.
In a related reaction, thioesters can be converted into esters.  Thioacetate esters can also be cleaved with methanethiol in the presence of stoichiometric base, as illustrated in the preparation of pent-4-yne-1-thiol:
A reaction unique to thioesters is the Fukuyama coupling, in which the thioester is coupled with an organozinc halide by a palladium catalyst to give a ketone.