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Digging into the mechanism of oxidative Pd(II)-catalyzed aminations

Abstract : Although the Pd(II)-catalyzed alkene aminopalladation and allylic C-H activation have been much described in literature, the in-depth mechanism of such type of process is far from being a simple matter. This account focuses on the oxidative intramolecular Pd(II)-catalyzed amination of unsaturated N-sulfonyl carbamates and carboxamides, revealing that different mechanistic paths can be operative. In particular, after activation of the unsaturation by Pd(II) catalyst, aminopalladation can take place, affording the corresponding high-energy cyclic (5- or 6-membered) aminopalladated intermediate (AmPI). This latter can evolve along different pathways, such as: distocyclic β-H elimination, oxidation by a strong terminal oxidant, or carbopalladation. Otherwise, the cyclic AmPI can lay dormant, in equilibrium with the initial substrate. In this case, alternative reactivities may take place, such as allylic C-H activation of the olefinic substrate, [3,3]-sigmatropic rearrangement, or decomposition.
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Mélanie M. Lorion, Fady Nahra, Vu Linh Ly, Carlo Mealli, Abdelatif Messaoudi, et al.. Digging into the mechanism of oxidative Pd(II)-catalyzed aminations. Chimica Oggi, Teknoscienze Srl, 2014, 32 (5), pp.30-35. ⟨hal-01089810⟩

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