Total Synthesis of Eleutherobin and Eleuthosides A and B K. C. Nicolaou T. Ohshima S. Hosokawa F. L. van Delft D. Vourloumis J. Y. Xu J. Pfefferkorn S. Kim 10.1021/ja9810639.s001 https://acs.figshare.com/articles/journal_contribution/Total_Synthesis_of_Eleutherobin_and_Eleuthosides_A_and_B/3670182 The total synthesis of the cytotoxic marine natural products eleutherobin (<b>1</b>) and eleuthosides A (<b>2</b>) and B (<b>3</b>) is described. The strategy involves glycosidation of the (+)-carvone-derived intermediate <b>7</b> with the arabinose-derived trichloroacetimidate <b>9</b> followed by base-induced ring closure and elaboration to afford the dihydroxy eneynone <b>19</b>. Selective hydrogenation of <b>19</b> led to the generation and intramolecular collapse of dienone <b>20 </b>furnishing <b>21</b> and thence <b>22</b> with the required structural framework of the target molecules. Finally, esterification with mixed anhydride <b>24</b> followed by deprotection gave eleutherobin (<b>1</b>) which served as a precursor to eleuthosides A (<b>2</b>) and B (<b>3</b>). The α-glycoside anomer of eleutherobin, compound <b>27</b>, was also synthesized by application of the developed chemistry, demonstrating the flexibility of the sequence in generating designed analogues for biological screening. 1998-08-13 00:00:00 Selective hydrogenation target molecules intramolecular collapse dienone 20 furnishing 21 eleuthoside cytotoxic marine anhydride 24 products eleutherobin Total Synthesis dihydroxy eneynone 19 compound 27