Nickel‐Catalyzed Domino Heck‐Type Reactions Using Methyl Esters as Cross‐Coupling Electrophiles

Abstract

While esters are frequently used as traditional electrophiles in substitution chemistry, their application in cross‐coupling chemistry is still in its infancy. This work demonstrates that methyl esters can be used as coupling electrophiles in Ni‐catalyzed Heck‐type reactions through the challenging cleavage of the C(acyl)−O bond under relatively mild reaction conditions at either 80 or 100 °C. With the σ‐NiII intermediate generated from the insertion of acyl NiII species into the tethered C=C bond, carbonyl‐retentive products were formed by domino Heck/Suzuki–Miyaura coupling and Heck/reduction pathways when organoboron and mild hydride nucleophiles are used.

Nickel-Catalyzed Heck Reaction

“…(I) Variably substituted methyl ortho-allyl benzoate has been analyzed as effective electrophile with 1-phenylethanol to synthesize cyclic products. Zheng et al 18 have devised mild reaction conditions to carry out such transformation taking Ni catalyst and K 3 PO 4 as base through Heck reaction.…”