Conversion of Triple Bonds into Single Bonds in a Domino Carbopalladation with Norbornene

A domino carbopalladation reaction of haloalkynes is presented. Remarkably, the four-time carbopalladation process converts the carbon-carbon triple bonds of haloalkynes stepwise into carbon-carbon double bonds, and finally to carbon-carbon single bonds. Features of this reaction are that the carbon-carbon double bonds of stable vinyl palladium intermediates are transformed into carbon-carbon single bonds with the generation of unstable alkyl palladium intermediates. The subsequently formed π-allylpalladium species are independently trapped by N-tosylhydrazones, boronic acids, and B2 pin2 in a highly diastereoselective manner, delivering the corresponding polycyclic and twisted products with a bicyclo[3.2.1]oct-2-en-3-yl)tricyclo[3.2.1.02,4 ]octane core skeleton in moderate to good yields via C-C and C-B bond formations. Significantly, the dual roles of norbornenes, ring construction and ring expansion, and the identification of electron-rich tri(2-furyl)phosphine as the ligand are found to be critical for the success of these transformations.