Well-Defined Dinuclear Gold Complexes for Preorganization-Induced Selective Dual Gold Catalysis.

Autor: Vreeken V; Homogeneous, Bioinspired and Supramolecular Catalysis, van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, The Netherlands., Broere DL; Homogeneous, Bioinspired and Supramolecular Catalysis, van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, The Netherlands., Jans AC; Homogeneous, Bioinspired and Supramolecular Catalysis, van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, The Netherlands., Lankelma M; Homogeneous, Bioinspired and Supramolecular Catalysis, van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, The Netherlands., Reek JN; Homogeneous, Bioinspired and Supramolecular Catalysis, van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, The Netherlands., Siegler MA; Small Molecule X-ray Crystallography Facility, Department of Chemistry, John Hopkins University, 3400 N. Charles St., Baltimore, MD, 21218, USA., van der Vlugt JI; Homogeneous, Bioinspired and Supramolecular Catalysis, van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, The Netherlands. j.i.vandervlugt@uva.nl.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2016 Aug 16; Vol. 55 (34), pp. 10042-6. Date of Electronic Publication: 2016 Jul 19.
DOI: 10.1002/anie.201603938
Abstrakt: 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 PN(H) P(iPr) (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 Au2 core. Facile reaction with phenylacetylene affords the σ,π-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 σ,π-activation with bifunctional substrates.
(© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Databáze: MEDLINE
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