Perylenequinone Natural Products: Evolution of the Total Synthesis of Cercosporin
- 9 November 2009
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 75 (1) , 44-56
- https://doi.org/10.1021/jo9013854
Abstract
The evolution of the first total synthesis of perylenequinone cercosporin is described. The key features developed during these efforts include a biscuprate epoxide alkylation, installation of the methylidene acetal, palladium-catalyzed O-arylation, and C3,C3′-decarbonylation. Due to the rapid atropisomerization of the helical axis of cercosporin (at 37 °C), the sequencing of these transformations was critical. To this end, the developed protocol enabled the formation of a key advanced intermediate on preparative scale absent any atropisomerization. Furthermore, the O-arylation proved to be general, and the strategy was used in an improved synthesis of a helical chiral perylenequinone structure.Keywords
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