(PPh3)AuCl/AgOTf-Catalyzed Intermolecular Hydroamination of Alkynes with Sulfonamides To Form N-Sulfonyl Imines

Cui, Dongmei; Zheng, Jia Wei; Yang, Liuyang; Zhang, Chen

doi:10.1055/s-0029-1219384

Cited by 11 publications

(4 citation statements)

References 6 publications

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“…As part of our ongoing studies on metal-catalyzed reactions, we have reported the hydroalkoxylation of allenes with alcohols and hydroamination of alkynes with sulfonamides in the presence of gold catalysts [26–28]. On the basis of these studies, in an initial experiment, 1-phenyl-1,2-propadiene ( 1a ) (1.5 mmol) was treated with 4-methylbenzenesufonamide ( 2a ) (0.5 mmol) in the presence of 2 mol % of (PPh 3 )AuCl and 8 mol % of AgOTf in dioxane at 70 °C efficiently to form linear adduct 3a in 43% yield (Table 1, entry 1).…”

Section: Resultsmentioning

confidence: 99%

Gold-catalyzed intermolecular hydroamination of allenes with sulfonamides

Zhang¹,

Zhang²,

Cai³

et al. 2013

Beilstein J. Org. Chem.

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Section: Resultsmentioning

confidence: 99%

Gold-catalyzed intermolecular hydroamination of allenes with sulfonamides

Zhang¹,

Zhang²,

Cai³

et al. 2013

Beilstein J. Org. Chem.

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“…However, the addition of N ‐nucleophiles proceeds differently, viz. primary‐ and secondary amines react smoothly and selectively, whereas ammonia and hydrazines, instead of the addition to target substrates, reduce gold(I) to colloid gold thus preventing the planned reaction. To avoid the poisoning of the catalyst via the reduction, usage of specifically designed ligands is required .…”

Section: Introductionmentioning

confidence: 99%

Gold‐Catalyzed Functionalization of Semicarbazides with Terminal Alkynes to Achieve Substituted Semicarbazones

et al. 2019

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Gold‐catalyzed functionalization of semicarbazides (ArNHCONHNH2) with various terminal alkynes R2C≡CH (R2 = Alk or Ar) in the presence of Ph3PAuNTf2 (3 mol‐%) grants a range of substituted semicarbazones (16 examples; 64–93 %). This novel metal‐catalyzed coupling proceeds under mild conditions (PhCl, 60 °C) and demonstrates a high functional group tolerance; the reaction is sensitive to the electronic effects of the substituents in terminal alkynes. Inspection of XRD solid‐state structures of three obtained semicarbazones proved their dimerization via weak to moderate strength hydrogen bonding. The structures of the semicarbazones in solutions were studied by concentration dependent 1H NMR and 2D NMR and these experiments proved the presence of H‐bonds between two molecules. The nature and energy of H‐bonding (3.8–5.1 kcal/mol), degree of electron density delocalization, and rotational barriers via various bonds in the equilibrium model structures were studied by DFT calculations at the M06‐2X/6‐311++G** level of theory.

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“…One of the reaction types that has been the focus of investigation with gold complexes is the nucleophilic addition of various functional groups to unsaturated substrates. , Earlier, gold(I) was found to be an active catalyst for the addition of different nucleophiles to alkynes and allenes; nevertheless the use of gold complexes in activating olefins was more limited…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Comparison of Acid- and Gold(I)-Catalyzed Nucleophilic Addition Reactions to Olefins

2010

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Density functional theory calculations were used to explore the mechanism of Me 3 PAuOTf (gold)-and TfOH (Brønsted acid)-catalyzed nucleophilic additions to olefins. Addition of N-and O-nucleophiles have been theoretically modeled by the reactions of CbzNH 2 (hydroamination) and PhOH (hydroalkoxylation) with ethene. Both gold(I) and Brønsted acids are shown to be active catalysts for the reaction. The gold-catalyzed mechanisms were found to be fully consistent with those proposed earlier for the hydroamination of dienes and hydroalkoxylation of alkenes. The gold(I)-catalyzed hydroamination was found to be stepwise, whereas the hydroalkoxylation was found to proceed via a concerted step. The TfOH-catalyzed process was found to be concerted.

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(PPh3)AuCl/AgOTf-Catalyzed Intermolecular Hydroamination of Alkynes with Sulfonamides To Form N-Sulfonyl Imines

Abstract: In the presence of a catalytic amount of (PPh 3 )AuCl and AgOTf, intermolecular hydroamination of unactivated alkynes with sulfonamides has been shown to proceed and give N-sulfonyl ketimines in medium to excellent yields.

Cited by 11 publications

References 6 publications

Gold-catalyzed intermolecular hydroamination of allenes with sulfonamides

Gold-catalyzed intermolecular hydroamination of allenes with sulfonamides

Gold‐Catalyzed Functionalization of Semicarbazides with Terminal Alkynes to Achieve Substituted Semicarbazones

Mechanistic Comparison of Acid- and Gold(I)-Catalyzed Nucleophilic Addition Reactions to Olefins

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