As a novel class of polyketides,indoxamycins A–F were isolated in 2009 by Sato group from saline cultures of marine-derived actinomycetes(Figure 1).[1] Within this family,indoxamycins A and F have been shown to display growth inhibition against HT-29 tumor cell lines(IC50 = 0.59 μM and 0.31 μM,respectively).These inhibition activities achieved the same level as that of mitomycin(IC50 = 0.66 μM).The skeleton of the molecules is characterized by an unprecedented [5,5,6] tricyclic carbon framework with six contiguous stereogenic centers,of which three are quaternary and two are vicinal.Their unusual structural architecture combined with the promising biological activities render the indoxamycins notable as targets for synthetic studies.[2] Herein,we will report our efforts on these natural products with new synthetic strategy from readily available building blocks.[3]