Development of Bifunctional Thiourea Organocatalysts Derived from a Chloramphenicol Base Scaffold and their Use in the Enantioselective Alcoholysis of meso Cyclic Anhydrides

The synthesis of new chloramphenicol‐base‐derived thiourea organocatalysts, (1 S ,2 R )‐ 12 a – f and (1 R ,2 R )‐ 15 a – c , and their use in the enantioselective alcoholysis of meso ‐anhydrides are described. In particular, hemiesters afforded excellent enantioselectivities if low loadings of (1 S ,2 R )‐ 12 a – f were used. Almost no enantioselectivities were achieved with the use of (1 R ,2 R )‐ 15 a – c . This technique was used to synthesize ( R )‐(−)‐baclofen.