Copper-Catalyzed γ-Selective and Stereospecific Direct Allylic Alkylation of Terminal Alkynes: Synthesis of Skipped Enynes


  • This work was supported by the Grants-in-Aid for Young Scientists (A), JSPS to H.O. and by CREST and ACT-C, JST to M.S. Y.M. thanks the JSPS for their scholarship support.


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Skipping out: The title reaction using internal secondary allylic phosphates proceeded with excellent γ regioselectivity and E stereoselectivity to give skipped enynes. Enantioenriched secondary allylic phosphates proceeded with 1,3-anti stereochemistry to afford the corresponding chiral 1,4-enynes, which were used for various derivatizations and the formal total synthesis of a GnRH antagonist. phen=1,10-phenanthroline.