Benzylic C–H activation and C–O bond formation via aryl to benzylic 1,4-palladium migrations

1,4‐Migration of Transition Metals in Organic Synthesis

“…In 2008, Kesharwani and Larock realized a benzylic C—H activation and oxygenation via an aryl to benzylic 1,4‐Pd migration. The reaction with 1‐iodo‐8‐methylnaphthalene 65 under the catalysis of Pd(OAc) 2 /dppm gave benzylic acyloxylation product 66 (Scheme ) . Under standard conditions, the reaction of 65 ‐ d 3 afforded 66 ‐ d 2 , and no any deuterium incorporation was observed in the aromatic ring.…”

Palladium-catalysed reactions of 6-halogeno-1,1′-binaphthyl derivatives. A detailed investigation of structure/reactivity and structure/selectivity relationships

“…18 Various aryl to aryl, 19 aryl to benzylic 20 and vinylic to aryl 21 palladium migrations have been described in the literature for biaryl compounds 19 or naphthalene derivatives. 20 Although according to DFT/B3LYP calculations of Dedieu, 22 various 1/n aryl-to-aryl palladium shifts (n¼3e6) are feasible, to the best of our knowledge, no such migrations involving binaphthyl derivatives have been reported before.…”

Migratory Decarboxylative Coupling of Coumarins: Synthetic and Mechanistic Aspects

“…First, decarboxylative metalation could produce an aryl palladium species that is capable of undergoing a 1,3-migration (path a). 11 Alternatively, the intermediate carboxylate may deprotonate the methyl group to generate a stabilized malonic acid dienolate. Such a proposal is reasonable given that the pK a values of carboxylates (~12 in DMSO) and malonates (~14 in DMSO) are comparable.…”