The efficient catalysis of transthioesterification reactions by a urea-based (but not thiourea-based) hydrogen bond donor in the presence of an amine co-catalyst has been demonstrated for the first time. The process is of wide substrate scope and the efficient exchange between unhindered achiral thiols and bulkier chiral thioesters is possible in the presence of the catalyst, which is a key first milestone towards the development of kinetic resolution processes based on transthioesterification processes.
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