Gold <i>versus</i> Silver‐Catalyzed Intermolecular Hydroaminations of Alkenes and Dienes

Giner, Xavier; Nájera, Carmén; Kovács, Gâbor; Lledós, Agustı́; Ujaque, Gregori

doi:10.1002/adsc.201100478

Cited by 44 publications

(16 citation statements)

References 94 publications

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“…DFT studies vigorously promoted the investigations of mechanism for Au(I)‐catalyzed hydroamination [59–62] and gave the general information of intermediate bonding, N‐nucleophile types in the dehydrogenation step and the energetics of the whole catalytic cycle. Based on the mechanism of gold(I) catalyzed hydroamination, [63–66] the triangular tri‐gold species were proposed to firstly interact with an terminal alkyne and form a catalytically active cationic Au(I)‐alkyne complex in situ.…”

Section: Resultsmentioning

confidence: 99%

Syntheses of Triangular Gold Complexes and Their Applications in Hydroamination Reaction

Sun

et al. 2021

Eur J Inorg Chem

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Triangular all‐metal complexes have aroused our research interest due to their unique structural and properties. Herein, through the facile reduction of μ3‐oxo complex [μ3‐O(PPh3Au)3]+BF4− (1), we synthesized and isolated the triphenylphosphine stabilized triangular tri‐gold complex [(PPh3Au)3]+BF4− (2) for the first time (yield=90 %). Both complexes showed interesting photochemical sensitivity to temperatures and solvents. The cyclic voltammetry of these complexes showed one single oxidation process in CH3CN. These tri‐gold complexes (2 mol % based on the complex itself) were further applied in the catalytic hydroaminations for substituted phenylacetylenes with anilines and gave the corresponding imine products with great catalytic reactivity and regioselectivity without aiding any promoters or additives. When the loading of the tri‐gold complexes was decreased to 1.0 mol%, 95 % and 97 % of conversions were obtained using 1 and 2, respectively. When further decreased the catalyst loading to 0.5 mol% in preparative scale, 83 % and 80 % of isolated yields were achieved, respectively. This method presented great significance for the syntheses of a series of imine‐containing pharmaceutical intermediates even in preparative scale. Moreover, the investigations of catalytic mechanisms of this reaction indicated that these tri‐gold complexes played important roles as efficient pre‐catalysts in hydroaminations.

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Section: Resultsmentioning

confidence: 99%

Syntheses of Triangular Gold Complexes and Their Applications in Hydroamination Reaction

Sun

et al. 2021

Eur J Inorg Chem

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“…The combined use of more electrophilic phosphite-gold complexes [ 41 – 42 ] and enabling techniques such as microwave irradiation [ 43 ] led to consistent improvement in efficiency of the catalytic system. In particular when (Ph 3 O)PAuOTf was employed under microwave irradiation with a catalyst loading as low as 0.05 mol %, the condensation of TsNH 2 to norbornene was realized in quantitative yield.…”

Section: Reviewmentioning

confidence: 99%

New developments in gold-catalyzed manipulation of inactivated alkenes

Chiarucci

Bandini

2013

Beilstein J. Org. Chem.

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SummaryOver the recent years, the nucleophilic manipulation of inactivated carbon–carbon double bonds has gained remarkable credit in the chemical community. As a matter of fact, despite lower reactivity with respect to alkynyl and allenyl counterparts, chemical functionalization of isolated alkenes, via carbon- as well as hetero atom-based nucleophiles, would provide direct access to theoretically unlimited added value of molecular motifs. In this context, homogenous [Au(I)] and [Au(III)] catalysis continues to inspire developments within organic synthesis, providing reliable responses to this interrogative, by combining crucial aspects such as chemical selectivity/efficiency with mild reaction parameters. This review intends to summarize the recent progresses in the field, with particular emphasis on mechanistic details.

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“…Homogeneous intermolecular hydroamination of vinyl arenes with weakly basic nitrogen sources such as sulfonamides has been catalyzed by the salts of metals including platinum, copper, bismuth, hafnium, iron, gold, silver, and zirconium. 2a-f However, most of these methods have shown limitations, especially with electron-rich vinyl arenes. These substrates, including methyl or methoxy-substituted styrenes, often furnished hydroamination products in low-to-intermediate yields along with large amounts of side products.…”

Section: Introductionmentioning

confidence: 99%

“…9a-b There have been several reasons for the dearth of these reactions, including the tendency of the nitrogen sources to buffer the effect of the acids as well as the acid-catalyzed formation of undesired homocoupling products from vinyl arene substrates. 2d,8 …”

Section: Introductionmentioning

confidence: 99%

Chemoselective hydroamination of vinyl arenes catalyzed by an NHC-amidate-alkoxide Pd(II) complex and p-TsOH

Giles

O’Neill

Lee

et al. 2013

Tetrahedron Letters

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The hydroamination of various substituted vinyl arenes with benzenesulfonamide was explored using an NHC-amidate-alkoxide palladium catalyst in conjunction with p-TsOH. Utilizing halide-substituted and electron-rich vinyl arenes, this methodology selectively furnished the cross-coupled hydroamination products in moderate to excellent yields in a Markovnikov fashion while greatly reducing undesired acid-catalyzed homocoupling of the vinyl arenes. Electron-rich vinyl arenes typically required milder conditions than electron-poor ones. While most effective for para-substituted substrates, the catalyst system also furnished the desired products from ortho- and meta-substituted vinyl arenes with high chemoselectivities.

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Gold versus Silver‐Catalyzed Intermolecular Hydroaminations of Alkenes and Dienes

Abstract: Comparative studies about the hydroamination of unactivated alkenes and dienes catalyzed by either cationic gold(I) triphenyl phosphite complexes or silver salts were performed using sulfon-

Cited by 44 publications

References 94 publications

Syntheses of Triangular Gold Complexes and Their Applications in Hydroamination Reaction

Syntheses of Triangular Gold Complexes and Their Applications in Hydroamination Reaction

New developments in gold-catalyzed manipulation of inactivated alkenes

Chemoselective hydroamination of vinyl arenes catalyzed by an NHC-amidate-alkoxide Pd(II) complex and p-TsOH

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