<i>anti</i>-Hydroarylation of Activated Internal Alkynes: Merging Pd and Energy Transfer Catalysis Javier Corpas Pablo Mauleón Ramón Gómez Arrayás Juan C. Carretero 10.1021/acs.orglett.0c02281.s001 https://acs.figshare.com/articles/journal_contribution/_i_anti_i_-Hydroarylation_of_Activated_Internal_Alkynes_Merging_Pd_and_Energy_Transfer_Catalysis/12749757 A general catalytic <i>anti</i>-hydroarylation of electron-deficient internal alkynes compatible with both electron-poor and electron-rich aryl reagents is reported. This selectivity is achieved through a sequential <i>syn</i>-carbopalladation of the alkyne by an Ar–Pd species, followed by a tandem, Ir-photocatalyzed, counter-thermodynamic <i>E</i> → <i>Z</i> isomerization. The use of <i>ortho</i>-substituted boronic acids enables direct access to pharmaceutically relevant heterocyclic cores via a cascade process. Mechanistic insight into the involvement of Ar–Pd versus Pd–H as an active species is provided. 2020-07-31 22:15:00 Hydroarylation sequential syn ortho selectivity heterocyclic cores Mechanistic insight species hydroarylation electron-rich aryl reagents access electron-poor Merging Pd counter-thermodynamic cascade process Activated Internal Alkynes pharmaceutically tandem involvement boronic acids Ir-photocatalyzed Energy Transfer Catalysis alkyne carbopalladation electron-deficient Ar isomerization