Catalytic Asymmetric Total Synthesis and Stereochemical Revision of Leucinostatin A: A Modulator of Tumor-Stroma Interaction.

Total synthesis of leucinostatin A, a modulator of tumor-stroma interactions, using asymmetric catalyses, a nitroaldol reaction, thioamide-aldol reaction, Strecker-type reaction, and alcoholysis of 3-methylglutaric anhydride, is described. We demonstrated the applicability of the established catalytic asymmetric processes to the synthesis of molecules with a complex structure. Careful analysis of the NMR data, HPLC profiles, and biological activity revealed that the correct structure of leucinostatin A is the epimeric form of the reported structure; the secondary alcohol within the AHMOD residue has an R configuration.