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Palladium-Catalyzed Chemoselective Activation of sp3 vs sp2 C-H Bonds: Oxidative Coupling To Form Quaternary Centers.

ABSTRACT: The oxidative activation of alkyl C-H bonds vs arene C-H bonds with Pd(OAc)2 has been found to be generalizable to a number of nucleophilic substrates allowing the formation of a range of hindered quaternary centers. The substrates share a common mechanistic path wherein Pd(II) initiates an oxidative dimerization. The resultant dimer modifies the palladium catalyst to favor activation of alkyl C-H bonds in contrast to the trends typically observed via a concerted metalation deprotonation mechanism. Notably, insertion occurs at the terminus of the alkyl arene for hindered substrates. Two different oxidant systems were discovered that turn over the process. Parameters have been identified that predict, which substrates are productive in this reaction.

SUBMITTER: Hong G

PROVIDER: S-EPMC6880961 | biostudies-literature | 2019 Apr

REPOSITORIES: biostudies-literature

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Palladium-Catalyzed Chemoselective Activation of sp3 vs sp2 C-H Bonds: Oxidative Coupling To Form Quaternary Centers.

Hong Gang G Nahide Pradip D PD Kumar Neelam Uday U Amadeo Peter P Vijeta Arjun A Curto John M JM Hendrick Charles E CE VanGelder Kelsey F KF Kozlowski Marisa C MC

ACS catalysis 20190308 4

The oxidative activation of alkyl C-H bonds vs arene C-H bonds with Pd(OAc)2 has been found to be generalizable to a number of nucleophilic substrates allowing the formation of a range of hindered quaternary centers. The substrates share a common mechanistic path wherein Pd(II) initiates an oxidative dimerization. The resultant dimer modifies the palladium catalyst to favor activation of alkyl C-H bonds in contrast to the trends typically observed via a concerted metalation deprotonat ...[more]

PMID: 31777683

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