2019
DOI: 10.1002/anie.201902838
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Carboxylate‐Assisted Oxidative Addition to Aminoalkyl PdII Complexes: C(sp3)−H Arylation of Alkylamines by Distinct PdII/PdIV Pathway

Abstract: We report the discovery of an approach to functionalize secondary alkylamines using 2-halobenzoic acids as aryl transfer reagents. These reagents promote an unusually mild carboxylateassisted oxidative addition to alkylamine-derived palladacycles. In the presence of Ag(I) salts, a decarboxylative C(sp 3)-C(sp 2) bond reductive elimination leads to γ-aryl secondary alkylamines and renders the carboxylate motif a traceless directing group. Stoichiometric mechanistic studies were effectively translated to a Pdcat… Show more

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Cited by 38 publications
(8 citation statements)
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“…Finally, oxidant-promoted reductive elimination of IV could build benzo-fused peripheral-substituted caprolactones (Figure ). Generally, intermediates of types I and II are prone to C-benzoxylation and decarboxylative arylation, respectively . We envisioned addressing the challenges depicted in Figure by considering the following parameters: (i) a suitable ligand to facilitate the CMD processes for the two C­(sp 3 )–H activation through Pd–arene interaction and (ii) a solvent mixture and an oxidant for preventing the decarboxylative arylation and making the C–O reductive elimination smooth.…”
Section: Introductionmentioning
confidence: 99%
“…Finally, oxidant-promoted reductive elimination of IV could build benzo-fused peripheral-substituted caprolactones (Figure ). Generally, intermediates of types I and II are prone to C-benzoxylation and decarboxylative arylation, respectively . We envisioned addressing the challenges depicted in Figure by considering the following parameters: (i) a suitable ligand to facilitate the CMD processes for the two C­(sp 3 )–H activation through Pd–arene interaction and (ii) a solvent mixture and an oxidant for preventing the decarboxylative arylation and making the C–O reductive elimination smooth.…”
Section: Introductionmentioning
confidence: 99%
“…Oxidative addition of C with aryl iodide 2 gives a Pd IV intermediate D , which selectively undergoes a C−I bond‐forming RE to give product E possibly due to the presence of weak coordination of the nitro group to the Pd metal center [28] . Of note, the oxidative addition step might also be promoted by the weak coordination of the nitro group to the Pd center [28c,d] . Thus, an electron‐donating group such as the methoxy is possible to enhance the weak coordination of nitro group, leading to more efficient oxidative addition and selective RE (see Supporting Information for the screening of aryl iodides).…”
Section: Resultsmentioning
confidence: 99%
“…Gaunt reported the use of 2-bromobenzoic acids as coupling partners for the γ-C(sp 3 )-H arylation of secondary amines. 78 The extra carboxylate coordination site on the aromatic coupling partner improved reactivity, and a decarboxylation event gave the arylated product (Scheme 26). 79 An amine directed cyclopalladation is proposed to give palladacycle A. Ligand exchange with the bromo carboxylic acid gave intermediate B in which the C-Br bond is forced close to the palladium centre, initiating oxidative addition to give Pd IV intermediate C. The silver source was proposed to abstract the halide, giving intermediate D which was active to a concerted decarboxylative 1,2-Pd migration/reductive elimination sequence to give 7-membered palladacyclic intermediate E (isolated and characterised by X-ray).…”
Section: C(sp 3 )-H Functionalisation Of Aminesmentioning
confidence: 99%