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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