A direct α‐acylation strategy of thioesters for the synthesis of α‐substituted monothiomalonates and β‐thioester‐Weinreb amides is described. Using carbonylimidazolides as acylating agents under LiHMDS‐mediated conditions, the method provides efficient access to a broad range of previously inaccessible derivatives, including α‐aryl analogs, in high yields without stoichiometric coupling reagents. The utility of the approach is demonstrated through gram‐scale reactions and diverse downstream functionalizations .
Ma et al. (Tue,) studied this question.
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