%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