Science of Synthesis

Li, X.; Song, Q., Science of Synthesis Knowledge Updates, (2024) 1, 313.

A commonly employed method to synthesize thiocarboxylic O-acid esters involves treating the corresponding carboxylic acid esters with a thionating agent such as phosphorus decasulfide (P4S10) or Lawesson’s reagent. Although this strategy suffers from some drawbacks, it is still one of the most reliable and straightforward synthetic approaches. For example, in 2015, Li and co-workers developed a system that combines phosphorus decasulfide with N,N-diethylaniline to efficiently convert carboxylic esters ‌1‌ into thionoesters ‌2‌ (‌Scheme 1‌).[‌2‌] The in situ generated Lawesson-type thionating reagent ‌3‌ plays a crucial role in this reaction; in the absence of the aniline, a sharp decrease in yield is observed.

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