Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 55, Issue 34, Pages 10042-10046Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201603938
Keywords
sigma,pi-activation; bridging acetylide; dinuclear gold complexes; dual gold catalysis; redox-active ligand
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Funding
- European Research Council (ERC) [279097]
- ERC [339786]
- European Research Council (ERC) [339786] Funding Source: European Research Council (ERC)
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The synthesis, reactivity, and potential of well-defined dinuclear gold complexes as precursors for dual gold catalysis are explored. Using the preorganizing abilities of the ditopic (PNPiPr)-P-H (L-H) ligand, dinuclear Au-I-Au-I complex 1 and mixed-valent Au-I-Au-III complex 2 provide access to structurally characterized chlorido-bridged cationic species 3 and 4 upon halide abstraction. For 2, this transformation involves unprecedented two-electron oxidation of the redox-active ligand, generating a highly rigidified environment for the Au-2 core. Facile reaction with phenylacetylene affords the sigma,pi-activated phenylacetylide complex 5. When applied in the dual gold heterocycloaddition of a urea-functionalized alkyne, well-defined precatalyst 3 provides high regioselectivities for the anti-Markovnikov product, even at low catalyst loadings, and outperforms common mononuclear Au-I systems. This proof-of-concept demonstrates the benefit of preorganization of two gold centers to enforce selective non-classical sigma,pi-activation with bifunctional substrates.
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