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On the Mechanism of Pd(0)-Catalyzed, Cu(I) Carboxylate-Mediated Thioorganic-Boronic Acid Desulfitative Coupling. A Non-innocent Role for Carboxylate Ligand.

ABSTRACT: Computational studies of the mechanism of the Pd-catalyzed, Cu(I)-carboxylate-mediated desulfitative coupling of thioorganics with boronic acids have determined that the requisite Cu(I)-carboxylate plays multiple important roles. The Cu(I)-carboxylate enhances both the transmetalation and the C-C reductive elimination steps: it acts as a reactive transmetalation center and it provides a vital carboxylate ligand. The carboxylate ligand functions not only as an activator for the boronic acid, but it also displaces a phosphine ligand at the palladium center generating a catalytically competent mono-phosphine-palladium intermediate.

SUBMITTER: Musaev DG

PROVIDER: S-EPMC2742425 | biostudies-literature | 2009 Jul

REPOSITORIES: biostudies-literature

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On the Mechanism of Pd(0)-Catalyzed, Cu(I) Carboxylate-Mediated Thioorganic-Boronic Acid Desulfitative Coupling. A Non-innocent Role for Carboxylate Ligand.

Musaev Djamaladdin G DG Liebeskind Lanny S LS

Organometallics 20090701 16

Computational studies of the mechanism of the Pd-catalyzed, Cu(I)-carboxylate-mediated desulfitative coupling of thioorganics with boronic acids have determined that the requisite Cu(I)-carboxylate plays multiple important roles. The Cu(I)-carboxylate enhances both the transmetalation and the C-C reductive elimination steps: it acts as a reactive transmetalation center and it provides a vital carboxylate ligand. The carboxylate ligand functions not only as an activator for the boronic acid, but ...[more]

PMID: 20161122

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