Computational Insight into a Gold(I) N-Heterocyclic Carbene Mediated Alkyne Hydroamination Reaction

Katari, Madanakrishna; Rao, Mitta Nageswar; Rajaraman, Gopalan; Ghosh, Prasenjit

doi:10.1021/ic2024605

Cited by 50 publications

(41 citation statements)

References 108 publications

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“…molecules in the proton transfer step,110,125,126,129 may be at work. Calculations also foresee good efficiency of the [(CAAC)Au] + catalyst for the hydroamination of phenylacetylene, although no experimental results of this reaction have been reported.…”

mentioning

confidence: 99%

Hydroamination of C–C Multiple Bonds with Hydrazine Catalyzed by N-Heterocyclic Carbene–Gold(I) Complexes: Substrate and Ligand Effects

et al. 2015

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In this work, we computationally address, from DFT calculations, mechanistic issues of the recently described hydroamination reactions catalyzed by (carbene) gold(I) complexes that use hydrazine as N-nucleophile. We have explored the hydrohydrazination of alkynes, alkenes, and allenes using three gold− carbene catalysts reported by Bertrand's and Hashmi's groups. Aspects such as the associative or dissociative nature of the ligand exchange between hydrazine and the substrate, the generation of the catalytically active π-complex, the inner-or outer-sphere mechanism for the nucleophilic attack, the nitrogen to carbon proton transfer or the relative importance of the ligand substitution, the nucleophile addition, and the proton transfer barriers in the catalytic cycle are analyzed in light of the DFT results, taking into account the nature of the carbene ligand and the substrate. The study can provide background for the design of further hydroamination reactions using simple small N-nucleophiles.

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confidence: 99%

Hydroamination of C–C Multiple Bonds with Hydrazine Catalyzed by N-Heterocyclic Carbene–Gold(I) Complexes: Substrate and Ligand Effects

et al. 2015

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“…[73][74][75][76] The catalytically actives peciesi sp reparedi ns itu on addition of 10 mol %A gBF 4 ,w hich generates an LAu + species by chloride abstraction. The formation of 10 is therefore ar eactioni nw hichao rganometallic complexa cts both as substrate and as catalyst.…”

Section: Resultsmentioning

confidence: 99%

Coinage Metal Complexes of Bis‐Alkynyl‐Functionalized N‐Heterocyclic Carbenes: Reactivity, Photophysical Properties, and Quantum Chemical Investigations

Kiefer

Bestgen

Gamer

et al. 2017

Chemistry A European J

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Bis-phenylpropynyl-functionalized imidazolium salts and their corresponding gold and copper N-heterocyclic carbene (NHC) complexes were prepared in order to investigate their potential application for the synthesis of heterometallic coinage metal compounds. By transmetalation reactions with different precious metal sources, including copper and silver phenylacetylides [MCCPh] (M=Cu, Ag), polynuclear compounds were obtained, which were further investigated for their photoluminescence properties. Additionally, one gold NHC complex was post-functionalized by autocatalytic hydration of the alkynyl side chains. Time-dependent DFT investigations of singlet electronic excitations in representative complexes revealed excited states of diverse character, as determined by the specific complex structure and metallophilic interactions.

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“…[74] Significantly enough, a series of gold(I) precatalysts (compounds 29-32) supported by 1,2,4-triazole-derived Nheterocyclic carbene ligands were found to be active for the hydroamination of terminal alkynes (Figure 8 and Scheme 10). [75] The proposed catalytic cycle involved a crucial intramolecular 1,3-proton transfer step, the barrier of which underwent significant reduction when assisted by adventitious H 2 O or by a PhNH 2 substrate relay processes. The mass spectrometric evidence pointed toward the formation of a solvent-coordinated [(NHC)Au(MeCN)] + type species as the initiating species for the hydroamination reaction, which was proposed to proceed via the alkyne-and amine-activation pathways.…”

Section: Hydroamination Of Terminal Alkynesmentioning

confidence: 99%

“…[29] The hydroamination reaction was observed to undergo Markovnikov-type addition, as indicated by the isolation and subsequent characterization of the reaction product. [75] Experimental support for the mechanism comes from the recent isolation and structural characterization of vinyl gold intermediates by Hashmi [76] in intramolecular alkyne hydroamination reactions. [29] The catalytic cycle, as mod-eled by the density functional theory, found the amine-activation pathway to be energetically favorable over alkyne activation.…”

Section: Hydroamination Of Terminal Alkynesmentioning

confidence: 99%

Studies of the Electronic Properties of N‐Heterocyclic Carbene Ligands in the Context of Homogeneous Catalysis and Bioorganometallic Chemistry

Kumar

Ghosh

2012

Eur J Inorg Chem

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N‐heterocyclic carbenes (NHCs) have been dominating the world of homogeneous catalysis in an unprecedented manner in the last two decades. Understanding the underlying reasons behind catalysis with NHC ligands has thus become of significant interest. Subscribing to this view, we strive to identify the key attributes of N‐heterocyclic carbene ligands through a combination of experimental and computational studies. Rational catalyst design, by appropriate functionalization of N‐heterocyclic carbene ligands to investigate their utility in a host of catalytically relevant transformations of interest to contemporary organic synthesis, is thus central to our efforts. From this perspective, a variety of C–C and C–N bond forming reactions, namely, the Suzuki–Miyaura, Sonogashira, and Hiyama cross‐couplings, the base‐free Michael additions, the alkene and alkyne hydroaminations, the formation of β‐enaminones from 1,3‐dicarbonyl compounds and primary amines, and the environmentally important ring‐opening polymerizations (ROP) of L‐lactides, which produce biodegradable polylactide polymers from renewable resources, have been studied. The metal–carbene interaction in these catalysts has been probed with the aid of computational studies, which suggest that strong σ‐donor N‐heterocyclic carbene ligands bind tightly to the metal center and thereby impart the much needed stability to these catalysts. Even going beyond catalysis, we investigated the potential of N‐heterocyclic carbene complexes in biomedical applications particularly for their antimicrobial and anticancer properties.

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Computational Insight into a Gold(I) N-Heterocyclic Carbene Mediated Alkyne Hydroamination Reaction

Cited by 50 publications

References 108 publications

Hydroamination of C–C Multiple Bonds with Hydrazine Catalyzed by N-Heterocyclic Carbene–Gold(I) Complexes: Substrate and Ligand Effects

Hydroamination of C–C Multiple Bonds with Hydrazine Catalyzed by N-Heterocyclic Carbene–Gold(I) Complexes: Substrate and Ligand Effects

Coinage Metal Complexes of Bis‐Alkynyl‐Functionalized N‐Heterocyclic Carbenes: Reactivity, Photophysical Properties, and Quantum Chemical Investigations

Studies of the Electronic Properties of N‐Heterocyclic Carbene Ligands in the Context of Homogeneous Catalysis and Bioorganometallic Chemistry

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