Total Synthesis and Structural Reassignment of Laingolide A

The asymmetric total synthesis of four diastereomers of laingolide A was achieved, which led to the unambiguous assignment of the stereochemistry of the natural product. The salient features of the convergent, fully stereocontrolled approach were a copper-catalysed stereospecific Kumada-type coupling, a Julia-Kocienski olefination and an RCM/alkene migration sequence to access the desired macrocyclic enamide.

Automated summary

The asymmetric total synthesis of four diastereomers of laingolide A enabled the unambiguous assignment of the natural product's stereochemistry. The key features of the convergent, fully stereocontrolled approach included a copper-catalysed stereospecific Kumada-type coupling, a Julia-Kocienski olefination, and an RCM/alkene migration sequence to obtain the desired macrocyclic enamide.