Intermolecular Heck Coupling with Hindered Alkenes Directed by Potassium Carboxylates

Pd(0)‐catalyzed Mizoroki‐Heck reactions traditionally exhibit poor reactivity with polysubstituted, unbiased alkenes. Intermolecular reactions with simple, all‐carbon tetrasubstituted alkenes are unprecedented. Here we report that pendant carboxylic acids, combined with bulky monophospine ligands on palladium, can direct the arylation of tri‐ and tetrasubstituted olefins. Quaternary carbons are established at high Fsp3 attached‐ring junctures and the carboxylate directing group can be removed after coupling. Carboxylate directivity prevents over‐arylation of the new, less substituted alkene, which can be diversified in subsequent reactions.

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