The present paper reports a remote carbon-to-carbon boryl migration via an intramolecular 1,4-B/Cu shift, which establishes an in situ stereospecific electrophilic trap on the alkene moiety. The synthetic application is developed to prepare functionalized cyclopentenes by means of a palladium-catalyzed regioselective intramolecular coupling that completes a strategic cyclopropanation and generates valuable structural bicyclic systems. The mechanism is characterized by DFT (density functional theory) calculations which showed that the 1,4-migration proceeds through an intramolecular, nucleophilic attack of the copper-alkyl moiety on the boron atom bonded to the C(sp2), leading to a 5-membered boracycle structure. The computation of the 1,3- and 1,4-B/Cu shifts is also compared as is the impact of the endo- or exocyclic alkene on the reaction kinetics.
Keywords: Simmons‐smith; bicycles; boryl migration; copper; mechanism.
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