November 2023

This study reports the chiral-auxiliary-controlled diastereoselective dehydrogenative coupling of diarylmethanes with amides by using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone as the oxidant. The scope of the proposed reaction is very broad, with a wide variety of substrates and nucleophiles being applicable. The chiral induction can be attributed to the coordination of the oxygen atom on the chiral auxiliary with the carbocation intermediates.

In this Account, we summarize the development of a new strategy for streamlined synthesis of tetrahydropyran-embedded macrolactones and its successful implementation to a 13-step synthesis of (–)-exiguolide and an 11-step synthesis of (+)-neopeltolide.1 Introduction2 Development of Macrocyclization/Transannular Pyran Cyclization Strategy3 Total Synthesis of (–)-Exiguolide4 Total Synthesis of (+)-Neopeltolide5 Conclusions