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Ligand-accelerated C-H activation reactions: evidence for a switch of mechanism.

ABSTRACT: Initial rate studies have revealed dramatic acceleration in aerobic Pd(II)-catalyzed C-H olefination reactions of phenylacetic acids when mono-N-protected amino acids are used as ligands. In light of these findings, systematic ligand tuning was undertaken, which has resulted in drastic improvements in substrate scope, reaction rate, and catalyst turnover. We present evidence from intermolecular competition studies and kinetic isotope effect experiments that implies that the observed rate increases are a result of acceleration in the C-H cleavage step. Furthermore, these studies suggest that the origin of this phenomenon is a change in the mechanism of C-H cleavage from electrophilic palladation to proton abstraction.

SUBMITTER: Engle KM

PROVIDER: S-EPMC2952432 | biostudies-literature | 2010 Oct

REPOSITORIES: biostudies-literature

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Ligand-accelerated C-H activation reactions: evidence for a switch of mechanism.

Engle Keary M KM Wang Dong-Hui DH Yu Jin-Quan JQ

Journal of the American Chemical Society 20101001 40

Initial rate studies have revealed dramatic acceleration in aerobic Pd(II)-catalyzed C-H olefination reactions of phenylacetic acids when mono-N-protected amino acids are used as ligands. In light of these findings, systematic ligand tuning was undertaken, which has resulted in drastic improvements in substrate scope, reaction rate, and catalyst turnover. We present evidence from intermolecular competition studies and kinetic isotope effect experiments that implies that the observed rate increas ...[more]

PMID: 20853838

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