Transition-metal-catalyzed cross-coupling of organohalides and organometallic reagents is a central reactivity paradigm for carbon–carbon bond formation in organic synthesis. The incorporation of an alkene as a third reaction partner (or “conjunctive reagent”) in cross-coupling reactions offers an exciting platform for rapidly assembling complex structures from simple starting materials. However, this type of reaction has remained difficult to realize for various reasons, including the robust nature of competitive two-component coupling, challenges in controlling regioselectivity, and the rapid rates of β-hydride elimination from key alkylmetal intermediates. In order to address these issues, our laboratory has developed a substrate directivity strategy, whereby a Lewis basic functional group proximal to an otherwise unactivated alkene moiety orchestrates key steps in catalysis through its coordination with the metal catalyst. This seminar will examine the genesis of this approach using palladium and nickel catalysis and discuss its evolution from one that is reliant on strongly coordinating removable auxiliaries to one that can directly employ weakly coordinating native functional groups.

Cross-coupling with three components and in three dimensions

2019 Fall National Meeting

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