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Abstract
The synthesis, reactivity, and potential of well-defined dinuclear gold complexes as precursors for dual-gold catalysis is explored. Using the preorganizing abilities of well-known wide bite angle diphosphine ligands, DBFPhos and DPEPhos, dinuclear Au(I)–Au(I) complexes 1 and 2 are used as precursors to form well-defined monocationic species with either a chlorido- or acetylido-ligand bridging the two gold centers. These compounds are active catalysts for the dual-gold heterocycloaddition of a urea-functionalized alkyne, and the preorganization of both Au-centers affords efficient σ,π-activation of the substrate, even at high dilution, significantly outperforming benchmark mononuclear catalysts.
Highlights
The catalytic activation of substrates using two gold centers has proven to be a valuable strategy for a wide range of transformations in the broader context of gold-mediated catalysis [1,2,3,4,5,6,7,8,9,10,11,12,13,14].Commonly, mono-gold catalysis relies on π-activation of a substrate by a cationicAu(I) center
We have recently reported the catalytic competence of well-defined dinuclear σ,π-alkynide complexes in dual-gold catalysis, highlighting the importance of two preorganized Au centers with respect to regioselectivity and activity for intramolecular hydroamination [19,20]
In order to eliminate such ligand-centered chemistry leading to structural reorganization, and to exploit more readily available diphosphine ligands, we investigated wide bite angle diphosphine ligands with
Summary
The catalytic activation of substrates using two gold centers has proven to be a valuable strategy for a wide range of transformations in the broader context of gold-mediated catalysis [1,2,3,4,5,6,7,8,9,10,11,12,13,14].Commonly, mono-gold catalysis relies on π-activation of a substrate (e.g., an alkene) by a cationicAu(I) center. Dual-gold catalysis, on the other hand, can lead to both σ- and π-activation (either of the same functional group within a substrate or of two separate functional groups) by two Au centers. We have recently reported the catalytic competence of well-defined dinuclear σ,π-alkynide complexes in dual-gold catalysis, highlighting the importance of two preorganized Au centers with respect to regioselectivity and activity for intramolecular hydroamination [19,20]. This was achieved using the ditopic tridentate ligand PNH PiPr (2,20 -bis(diisopropylphosphino)-4,40 -ditolylamine) (Figure 1). In order to eliminate such ligand-centered chemistry leading to structural reorganization, and to exploit more readily available diphosphine ligands, we investigated wide bite angle diphosphine ligands with
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