Highly Selective Acylation of Dimethylamine Mediated by Oxygen Atoms on Metallic Gold Surfaces

Xu, Bingjun; Zhou, Ling; Madix, Robert J.; Friend, Cynthia M.

doi:10.1002/anie.200905642

Cited by 79 publications

(77 citation statements)

References 30 publications

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“…When formaldehyde is introduced, it inserts into the surface-amide bond and β-hydride elimination occurs to produce the formamide (Scheme 32). A similar mechanism was proposed by Friend for gold surfaces (Scheme 32) [53]. One important distinction between these two mechanisms is that gold requires ozone (O 3 ) to introduce adsorbed oxygen, while silver can employ oxygen (O 2 ).…”

Section: Catalytic Formylation With Metal Catalystsmentioning

confidence: 63%

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Formylation of Amines

2014

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Section: Catalytic Formylation With Metal Catalystsmentioning

confidence: 63%

“…Formylation of dimethylamine with formaldehyde on silver and gold surfaces was studied collaboratively by Madix and Friend [52,53]. Oxygen assisted formylation of dimethylamine on metallic silver surfaces was reported by Madix [52].…”

Section: Catalytic Formylation With Metal Catalystsmentioning

confidence: 99%

Formylation of Amines

2014

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“…In addition, it is known that adsorbed O on Au surfaces can activate N-H bonds [63]. Consistent with the general mechanism for O-assisted coupling on Au surfaces, after N-H bond activation of a reactant amine by the O/Au(111) surface, the adsorbed amide moiety attacks the electron-deficient carbonyl carbon in an adsorbed aldehyde, which can either be formed from β-H elimination of an alcohol or introduced directly (figure 14) [53,54,64]. This results in the formation of a hemiaminal intermediate, which undergoes β-H elimination to form the final amide product.…”

Section: Competitive Reactions Pathways: Controlling Selectivitymentioning

confidence: 82%

Catalyst design for enhanced sustainability through fundamental surface chemistry

Personick

Montemore

Kaxiras

et al. 2016

Phil. Trans. R. Soc. A.

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Decreasing energy consumption in the production of platform chemicals is necessary to improve the sustainability of the chemical industry, which is the largest consumer of delivered energy. The majority of industrial chemical transformations rely on catalysts, and therefore designing new materials that catalyse the production of important chemicals via more selective and energy-efficient processes is a promising pathway to reducing energy use by the chemical industry. Efficiently designing new catalysts benefits from an integrated approach involving fundamental experimental studies and theoretical modelling in addition to evaluation of materials under working catalytic conditions. In this review, we outline this approach in the context of a particular catalyst-nanoporous gold (npAu)-which is an unsupported, dilute AgAu alloy catalyst that is highly active for the selective oxidative transformation of alcohols. Fundamental surface science studies on Au single crystals and AgAu thin-film alloys in combination with theoretical modelling were used to identify the principles which define the reactivity of npAu and subsequently enabled prediction of new reactive pathways on this material. Specifically, weak van der Waals interactions are key to the selectivity of Au materials, including npAu. We also briefly describe other systems in which this integrated approach was applied.

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“…On the other hand, Friend et al. proposed the existence of a hemiaminal intermediate in the reaction of dimethylamine and formaldehyde on the surface of O/Au 44. Also, a hemiaminal intermediate has been considered in a reaction on a silver catalyst 45…”

Section: Other Oxidation Reactionsmentioning

confidence: 99%

Aerobic Oxidations Catalyzed by Colloidal Nanogold

Tsukuda

Tsunoyama

Sakurai

2011

Chemistry An Asian Journal

176

137

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Recently, dispersions of gold nanoclusters in liquid media (colloidal nanogold) have been extensively used as quasi-homogeneous catalysts for various aerobic oxidation reactions. This review describes recent progress in such reactions, with a focus on our comprehensive studies on gold clusters (<2 nm) stabilized by poly(N-vinyl-2-pyrrolidone) and their participation in oxidation reactions of alcohols, α-hydroxylation reactions of benzylic ketones, and homocoupling reactions of organoboronates, as well as formal Lewis acidic reactions, such as intramolecular hydroalkoxylation and hydroamination reactions of nonactivated alkenes. Mechanistic studies have shown that a partial electron transfer from the gold clusters to O(2) generates superoxide- or peroxide-like species and Lewis acidic centers, both of which play essential roles in the catalytic reactions.

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Highly Selective Acylation of Dimethylamine Mediated by Oxygen Atoms on Metallic Gold Surfaces

Cited by 79 publications

References 30 publications

Formylation of Amines

Formylation of Amines

Catalyst design for enhanced sustainability through fundamental surface chemistry

Aerobic Oxidations Catalyzed by Colloidal Nanogold

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