Palladium-catalyzed cross-coupling reactions with unactivated alkyl iodides can provide a novel entry into tetrasubstituted olefins when interrupted by a tandem alkyne insertion. Palladium mediated cross-couplings reactions of Csp2-carbon centers play an important role in modern organic chemistry due to their wide scope across a variety of substrates. Csp3-carbon electrophiles lack the generality of Csp2 cross-coupling reactions on account of difficult oxidative addition and facile �-hydride elimination. One possible solution to prevent �-hydride elimination focuses on utilizing the intermediate organopalladium species prior to �-hydride elimination. Here we describe the ability of a tethered alkyne to outcompete �-hydride elimination with rapid migratory insertion. The newly formed vinyl palladium can be used in subsequent cross-coupling chemistry.

Intercepting carbopalladium species prior to �-hydride elimination: New reactions in palladium-mediated cross couplings

246th National Meeting (2013)

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