%0 Journal Article %A Yang, Hua %A Carter, Rich G. %D 2010 %T Development of an Enantioselective Route toward the Lycopodium Alkaloids: Total Synthesis of Lycopodine %U https://acs.figshare.com/articles/journal_contribution/Development_of_an_Enantioselective_Route_toward_the_i_Lycopodium_i_Alkaloids_Total_Synthesis_of_Lycopodine/2744857 %R 10.1021/jo100916x.s003 %2 https://ndownloader.figshare.com/files/4423438 %K Total Synthesis %K Lycopodium Alkaloids %K sulfone rearrangement %K intramolecular Michael addition %K Key steps %K facilitiates enantioselective %K product family %K tricyclic core ring system %K Synthetic work %K keto sulfone %K intramolecular Michael additions %K Enantioselective Route %K alkaloid lycopodine %X Synthesis of a C15-desmethyl tricycle core of lycopodine has been accomplished. Key steps in the synthetic sequence include organocatalytic, intramolecular Michael addition of a keto sulfone and a tandem 1,3-sulfonyl shift/Mannich cyclization to construct the tricyclic core ring system. Synthetic work toward this natural product family led to the development of N-(p-dodecylphenylsulfonyl)-2-pyrrolidinecarboxamide, an organocatalyst which facilitiates enantioselective, intramolecular Michael additions. A detailed mechanistic discussion is provided for both the intramolecular Michael addition and the sulfone rearrangement. Finally, the application of these discoveries to the enantioselective total synthesis of alkaloid lycopodine is described. %I ACS Publications