Stoichiometric Reductive CN Bond Formation of Arylgold(III) Complexes with N‐Nucleophiles

Abstract

Abstract:The reductive formation of substituted anilines from amines and three well-defined aryl-, and chlorobis(triphenylphosphine)phenylgold-A C H T U N G T R E N N U N G (III) chloride (4) was studied. The reaction is stoichiometric in gold and represents a key step of a potential gold-catalyzed intermolecular amination reaction of arenes. It proceeds smoothly with a broad range of N-nucleophiles in the presence of sodium acetate (NaOAc) and enables the selective formation of N-substituted anilines in good yields. A mechanistic pathway is proposed and discussed as well.

Stoichiometric to catalytic reactivity of the aryl cycloaurated species with arylboronic acids: insight into the mechanism of gold-catalyzed oxidative C(sp2)–H arylation

“…The reaction of [AuCl 2 (Ph)(tpy)] ( 8 ) could not discriminate between the two. The gold( iii ) complex 8 could be prepared by the modified method of Fuchita et al 15 d and Limbach et al , 26 involving the auration of benzene with AuCl 3 and subsequent coordination with 1a . The structure of complex 8 was demonstrated by X-ray crystallographic analysis (Fig.…”

AuI/AuIII Catalysis: An Alternative Approach for CC Oxidative Coupling

“…Reacting the phenyl and xylyl substrates 17 a and 17 b with phenylacetylene in THF at 50 8C for 5 h led to diarylacetylenes 18 a and 18 b in 82 and 94 % yield respectively (Scheme 8). [24] Initial attempts to develop a catalytic version of this transformation directly from arenes and alkynes proved unsuccessful using a variety of external oxidants. [25] Instead, these reactions afforded styrene compounds resulting from a redox-neutral hydroarylation process as the only isolable products.…”

Controlling the oxidative addition of aryl halides to Au(I)

“…Although gold is able to undergo transmetallation, insertion, and reductive elimination reactions, the Au(I)→Au(III) oxidative addition remains comparatively highly elusive . In this regard, no direct evidence for oxidative addition of C sp2 X bonds at a single gold center has been obtained so far, (For a computational study of C sp2 −F bond activation at gold, see Ref.…”