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Stereoselective Access to ( E)-1,3-Enynes through Pd/Cu-Catalyzed Alkyne Hydrocarbation of Allenes
Louis Jeanne-Julien1, Guillaume Masson1, Remy Kouoi1
1C-TAC , UMR 8038, CNRS- Université de Paris, Faculté de Pharmacie , 4, avenue de l'Observatoire , 75006 , Paris , France.
Abstract:
PdII and CuI cooperate in catalyzing the alkynes hydrocarbation of allenes (AHA) giving ( E)-1,3-enynes with high yields, atom economy, and high regio-/stereoselectivities. We devised new efficient conditions and expanded the substrate scope. Experimental and computational studies support a nonorthodox PdII/PdIV catalytic cycle involving an oxidative addition triggered by a stereodeterminant H+ transfer. This reaction is leveraged in a new strategy of stereoselective synthesis of 1,3-dienes.
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