[C^N]‐Alkenyl Gold(III) Complexes by Proximal Ring‐Opening of (2‐Pyridyl)alkylidenecyclopropanes: Mechanistic Insights

González, Jorge A.; Verdugo, Felipe; Mascareñas, José L.; López, Fernándo; Nevado, Cristina

doi:10.1002/anie.202007371

Cited by 12 publications

(8 citation statements)

References 116 publications

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“…Efforts to improve the conversion of 1 to 3 were unsuccessful, and so we investigated C–C oxidative additions and carbonylations of other strained rings. Exposure of cyclopropanes 2b – e to 1 led to decomposition, with no evidence for the formation of C–C oxidative addition products . Similar results were obtained using MeDalPhosAuCl or IPrAuCl in place of 1 .…”

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confidence: 73%

Migratory Insertion of CO into a Au–C Bond

et al. 2022

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A MeDalPhos-ligated gold(III) metallafluorene complex, generated via C–C oxidative addition of biphenylene, reacts with CO to produce 9-fluorenone. Experimental and computational studies show that this proceeds via a hitherto unknown migratory insertion of CO into a Au(III)–C bond. This process is more energetically challenging compared to other M–C bonds, but once achieved, the product is comparatively stable with respect to retro-carbonylation. Exploiting migratory insertion of CO into Au–C bonds may extend the range of products that are accessible using gold chemistry.

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confidence: 73%

Migratory Insertion of CO into a Au–C Bond

et al. 2022

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“…The reaction involves cleavage of the proximal single C−C bond of the cyclopropyl moiety in a concerted process that resembles σ-bond metathesis. The Au(III) chelates catalyze the hydroarylation of styrenes …”

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confidence: 99%

Recent Advances in Gold(III) Chemistry: Structure, Bonding, Reactivity, and Role in Homogeneous Catalysis

2020

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Over the last decade the organometallic chemistry of gold(III) has seen remarkable advances. This includes the synthesis of the first examples of several compound classes that have long been hypothesized as being part of catalytic cycles, such as gold(III) alkene, alkyne, CO and hydride complexes, and important catalysis-relevant reaction steps have at last been demonstrated for gold, such as migratory insertion and β-H elimination reactions. Also, reaction pathways that were already known, such as the generation of gold(III) intermediates by oxidative addition and their reductive elimination, are much better understood. A deeper understanding of fundamental organometallic reactivity of gold(III) has also revealed unexpected mechanistic avenues, which can open when the barriers for reactions that for other metals would be regarded as "standard" are too high. This review summarizes and evaluates these developments, together with applications of gold(III) in synthesis and catalysis, with emphasis on the mechanistic insight gained in these investigations.

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“…Next, the feasibility of oxidative addition of vinyl iodides to gold was explored ( Scheme 2 ). 16 First, the (P,N)AuCl complex 1 was activated by AgSbF 6 and reacted with trans iodo styrene 4a . The corresponding (P,N)Au( iii ) vinyl complex 5a was immediately and cleanly formed, as apparent from NMR spectroscopy.…”

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confidence: 99%