Au(III) catalyzes the cross-coupling between activated methylenes and alkene derivatives

Abstract

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Spectroscopic Manifestations and Implications for Catalysis of Quasi‐d10Configurations in Formal Gold(III) Complexes

“…With this understanding in hand, we can appreciate how the +III OS of gold can constitute an active catalyst, where the a priori assumption that a gold(I) species is formed via in situ reduction may be misleading. These conclusions echo those recently drawn by Lopez and co‐workers [32] …”

“…For example, gold‐catalyzed reactions, where gold acts electrophilically as a Lewis acid (as distinct from stoichiometric or catalytic transformations where the OS of gold changes e.g., gold(I)/gold(III) couples), [5, 6, 30] it has been proposed that gold(III) is a precatalyst, transforming into the active gold(I) species through in situ reduction [31] . While it was a prominent idea in the earlier days of the field, this hypothesis has not been further discussed much, until being recently questioned [32] . Notably too, high‐valent complexes have previously been shown to be competent catalysts in their own right, retaining their +III oxidation state in situ [15a] .…”

On the mechanism of the Au(I)‐mediated addition of alkynes to anthranils to furnish 7‐acylindoles

“…It is worth noting that Au(III) species also catalyze a similar transformation, although the final outcome seems strongly dependent on the counterion chaperoning gold. [ 6,14,15 ]…”

Spectroscopic Manifestations and Implications for Catalysis of Quasi‐d10Configurations in Formal Gold(III) Complexes

“…[31] While it was a prominent idea in the earlier days of the field, this hypothesis has not been further discussed much, until being recently questioned. [32] Notably too, high‐valent complexes have previously been shown to be competent catalysts in their own right, retaining their +III oxidation state in situ. [15a] The computational and spectroscopic analysis presented here should dismiss the in situ reduction suggestion, as clear differences between the electronic structures of gold(I) and gold(III) centers were found both computationally and spectroscopically.…”