A catalytic chemo-, regio-, and enantioselective allylation of ketones with 1,3 dienes in the presence of (R,R)-Ph-BPE ligated Cu catalyst and hydrosilane is presented. This method provides a straightforward and alternative avenue to synthesize chiral homoallylic tertiary alcohols with 1,3-dienes as the latent allylic nucleophiles and avoids the traditional reliance on stoichiometric quantities of allylmetal reagents. This transformation proceeds under very mild conditions and displays good functional group tolerance and could be performed on a gram-scale.

A catalytic defluorinative hydroarylation of alkenes with polyfluoroarenes in the presence of dppbz-ligated Cu catalyst and silanes was developed. This method provides a straightforward and alternative avenue to synthetic important polyfluorinated arenes with readily available and bench-stable alkenes as latent nucleophiles, and therefore avoids conventional reliance on stoichiometric quantities of organometallic reagents. This reaction proceeds under very mild conditions and exhibits good functional group compatibility and high level of regioselectivity. The synthetic potential of this method was further demonstrated by a gram-scale synthesis, and an array of experimental studies were also carried out to elaborate the probable mechanism.

We herein report the copper-catalyzed asymmetric conjugate addition of β-substituted alkenyl heteroarenes, the one of most challenging Michael acceptors, with alkenes as the latent nucleophiles. Diverse chiral heteroarenes bearing two vicinal stereocenters were obtained in good to excellent yields, generally excellent enantioselectivity, and a good level of diastereoselectivity. The products of the Michael addition can be readily transformed into other valuable acyclic enantioenriched structures bearing three contiguous stereocenters via chiral amine catalysis. Mechanistic studies, including an isotope labeling experiment, a nonlinear effect study, kinetic isotope effect experiments, and initial-rate kinetics studies, were implemented, and the experimental results indicated that the hydrocupration step might be the turnover-limiting step. Moreover, the origin of preferential alkene hydrocupration in the presence of β-substituted alkenyl heteroarenes and the Ph-BPE-ligated CuH catalyst was also elucidated via some control experiments.

A catalytic defluorinative hydroarylation of alkenes with polyfluoroarenes in the presence of dppbz-ligated Cu catalyst and silanes was developed. This method provides a straightforward and alternative avenue to synthetic important polyfluorinated arenes with readily available and bench-stable alkenes as latent nucleophiles, and therefore avoids conventional reliance on stoichiometric quantities of organometallic reagents. This reaction proceeds under very mild conditions and exhibits good functional group compatibility and high level of regioselectivity. The synthetic potential of this method was further demonstrated by a gram-scale synthesis, and an array of experimental studies were also carried out to elaborate the probable mechanism.

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