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Well‐Defined Dinuclear Gold Complexes for Preorganization‐Induced Selective Dual Gold Catalysis
Author(s) -
Vreeken Vincent,
Broere Daniël L. J.,
Jans Anne C. H.,
Lankelma Marianne,
Reek Joost N. H.,
Siegler Maxime A.,
van der Vlugt Jarl Ivar
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201603938
Subject(s) - phenylacetylene , chemistry , cationic polymerization , bifunctional , catalysis , ligand (biochemistry) , combinatorial chemistry , cycloisomerization , alkyne , acetylide , salt metathesis reaction , redox , markovnikov's rule , reactivity (psychology) , photochemistry , metathesis , polymer chemistry , organic chemistry , regioselectivity , medicine , biochemistry , polymer , receptor , alternative medicine , pathology , polymerization
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 Au 2 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.