Biomimetic Total Synthesis of (−)-Isatisine A

The biomimetic total synthesis of (-)-isatisine A, a novel alkaloid with an unprecedented fused tetracyclic skeleton, was accomplished in 8 steps from indole and 4,6-O-isopropylidene-protected glucal. The synthesis features a convergent synthetic strategy which relies on nucleophilic addition and a biomimetic benzilic ester rearrangement as key reactions.