A synthetic route toward leucinostatin A, a modulator of tumor-stroma interactions, was established, in which catalytic asymmetric reactions developed in this laboratory were employed: nitroaldol reaction for the synthesis of HyLeu, thioamide-aldol reaction, Strecker-type reaction, and alcoholysis of 3-methylglutaric anhydride for the synthesis of AHMOD. Careful analysis of the NMR data, HPLC profiles, and biologic activity suggested 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 (epi-1).
