111. Bioinspired Total Synthesis of Homodimericin A

Jun Huang, Yueqing Gu, Kai Guo, Lei Zhu, Yu Lan*, Jianxian Gong* and Zhen Yang*

Angew. Chem. Int. Ed. 2017,  56, 7890

• Highlighted in Synfacts, 2017, 13, 906.

Homodimericin A is a remarkable fungal metabolite, and a highly oxygenated and racemic unsaturated polyketide. It poses a significant synthetic challenge due to its sterically demanding central cage-like core bearing eight contiguous stereogenic centers (including three contiguous all-carbon quaternary stereocenters), and several carbonyl functionalities. Based on its proposed biogenetic synthesis, we designed a bioinspired total synthesis of homodimericin A that proceeds in seven steps, featuring a double Michael reaction, an intramolecular Diels-Alder reaction, and an ene reaction.