Dormant versus Evolving Aminopalladated Intermediates: Toward a Unified Mechanistic Scenario in Pd-II-Catalyzed Aminations

Pd-II-catalyzed alkene aminopalladation and allylic C-H activation are two competing reaction sequences sharing the same reaction conditions. This study aimed at understanding the factors that bias one or the other path in the intramolecular oxidative cyclization of two types of N-tosyl amidoalkenes...

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Bibliographic Details
Published inChemistry : a European journal Vol. 20; no. 6; pp. 1539 - 1546
Main Authors Rajabi, Jamshid, Lorion, Melanie M., Vu Linh Ly, Liron, Frederic, Oble, Julie, Prestat, Guillaume, Poli, Giovanni
Format Journal Article
LanguageEnglish
Published WEINHEIM Wiley 03.02.2014
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
C-H ALKYLATION
ORGANIC-SYNTHESIS
AEROBIC OXIDATIVE AMINATION
PLATINUM(II) COMPLEXES
aminopalladation
ALLYLIC AMINATION
HYDROCARBON OXIDATION
C-H activation
DICATIONIC PALLADIUM(II)
[3,3]-sigmatropic rearrangement
beta-hydride elimination
palladium
HIGHLY ELECTROPHILIC SITE
TERMINAL OLEFINS
HYPERVALENT IODINE REAGENTS
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Summary:Pd-II-catalyzed alkene aminopalladation and allylic C-H activation are two competing reaction sequences sharing the same reaction conditions. This study aimed at understanding the factors that bias one or the other path in the intramolecular oxidative cyclization of two types of N-tosyl amidoalkenes. The results obtained are in accord with the initial generation of a high-energy cyclic (5- or 6-membered) aminopalladated intermediate. However, this latter species can evolve only if the following specific conditions are met: the availability of distocyclic beta-H elimination pathway, the presence of a strong terminal oxidant, or the availability of a carbopalladation pathway. Conversely, the cyclic alkylpalladium complex is only a latent species in equilibrium with the initial substrate and cannot evolve. Such a reactivity hurdle leaves the way open for alternative reactivities such as allylic C-H activation of the olefinic substrate to generate a eta(3)-allyl complex followed by its interception by the nitrogen nucleophile, [3,3]-sigmatropic rearrangement, or decomposition. This study proposes a unifying mechanistic picture that connects these competing mechanisms.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201302744