%0 Generic %A Yang, Luo %A Zheng, Qi-Yu %A Wang, De-Xian %A Huang, Zhi-Tang %A Wang, Mei-Xiang %D 2008 %T Reversal of Nucleophilicity of Enamides in Water: Control of Cyclization Pathways by Reaction Media for the Orthogonal Synthesis of Dihydropyridinone and Pyrrolidinone Clausena Alkaloids %U https://acs.figshare.com/articles/dataset/Reversal_of_Nucleophilicity_of_Enamides_in_Water_Control_of_Cyclization_Pathways_by_Reaction_Media_for_the_Orthogonal_Synthesis_of_Dihydropyridinone_and_Pyrrolidinone_i_Clausena_i_Alkaloids/2933047 %R 10.1021/ol800740h.s003 %2 https://acs.figshare.com/ndownloader/files/5339965 %K enamide %K endo %K Cyclization Pathways %K Pyrrolidinone Clausena Alkaloids %K Bu t OH %K intramolecular cyclization %K reversal %K nucleophilic reaction %K Orthogonal Synthesis %K Reaction Media %X A highly efficient, metal-free, and divergent method for the synthesis of 3,4-dihydropyridin-2-one and pyrrolidin-2-one Clausena alkaloids and their analogs is reported. While the oxirane-containing enamides underwent the TFA-mediated 6-endo-enamide-epoxide cyclization reaction in ButOH to produce homoclausenamides, an unprecedented nucleophilic reaction occurred at the α-carbon of enamides in water to yield 5-endo-enamide-epoxide cyclization products in excellent yields. The reversal of nucleophilicity of enamides in intramolecular cyclization is discussed in terms of steric and electronic effects of the oxirane-containing enamides. %I ACS Publications