Palladium‐Catalyzed Amination of Aryl Halides

Hartwig, John F.; Shaughnessy, Kevin H.; Shekhar, Shashank; Green, Rebecca A.

doi:10.1002/0471264180.or100.14

Cited by 23 publications

(28 citation statements)

References 264 publications

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“…The negative charge on the nitrogen is directly correlated to the rate of the elimination reduction (Figure 5). [46] Figure 1. Highly used drugs with N-heterocyclic core.…”

Section: Buchwald-hartwig Aminationmentioning

confidence: 99%

Ullmann‐Goldberg and Buchwald‐Hartwig C−N Cross Couplings: Synthetic Methods to Pharmaceutically Potential N‐Heterocycles

et al. 2021

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The Carbon-Nitrogen bond formation has always been an important and useful tool in drug discovery. Its wide applications in synthesizing N-heterocycles, known as the most prevalent moiety in the active pharmacophores, have attracted increasing attention from researchers. In recent years many works were devoted to finding new and more rapid and effective chemo-and regio-selective methods for the synthesis of N-containing heterocycles. Buchwald-Hartwig and Ullman-Goldberg are two proven efficient methods for synthesizing five, six, and seven-membered heterocycles found abundantly in literature. Here, we study these two amination methods more precisely, based on the reaction conditions and the products.

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“…The negative charge on the nitrogen is directly correlated to the rate of the elimination reduction (Figure 5). [46] Figure 1. Highly used drugs with N-heterocyclic core.…”

Section: Buchwald-hartwig Aminationmentioning

confidence: 99%

Ullmann‐Goldberg and Buchwald‐Hartwig C−N Cross Couplings: Synthetic Methods to Pharmaceutically Potential N‐Heterocycles

et al. 2021

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“…Most examples of such couplings have been reported with different palladium catalytic systems and aryl halides as coupling partners at higher reaction temperatures . Hartwig et al, , Shaughnessy et al, and a few others have reported ambient-temperature protocols for the above transformation; however, chloroheteroarenes as coupling partners have seldom performed at such low temperatures. The catalytic efficiency of the Cu(II)/PTABS system was therefore tested for a range of primary alkyl amines at ambient temperature.…”

Section: Resultsmentioning

confidence: 99%

Room-Temperature Amination of Chloroheteroarenes in Water by a Recyclable Copper(II)-Phosphaadamantanium Sulfonate System

Parmar¹,

Somvanshi

Kori

et al. 2021

J. Org. Chem.

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Buchwald–Hartwig amination of chloroheteroarenes has been a challenging synthetic process, with very few protocols promoting this important transformation at ambient temperature. The current report discusses about an efficient copper-based catalytic system (Cu/PTABS) for the amination of chloroheteroarenes at ambient temperature in water as the sole reaction solvent, a combination that is first to be reported. A wide variety of chloroheteroarenes could be coupled efficiently with primary and secondary amines as well as selected amino acid esters under mild reaction conditions. Catalytic efficiency of the developed protocol also promotes late-stage functionalization of active pharmaceutical ingredients (APIs) such as antibiotics (floxacins) and anticancer drugs. The catalytic system also performs efficiently at a very low concentration of 0.0001 mol % (TON = 980,000) and can be recycled 12 times without any appreciable loss in activity. Theoretical calculations reveal that the π-acceptor ability of the ligand PTABS is the main reason for the appreciably high reactivity of the catalytic system. Preliminary characterization of the catalytic species in the reaction was carried out using UV–VIS and ESR spectroscopy, providing evidence for the Cu(II) oxidation state.

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“…The synthesis of adamantane-containing 4,6-diaminopyrimidines was studied using a model compound 5a with Pd(dba) 2 as a precatalyst (Scheme 4, Table 1). Classical phosphine ligands, like BINAP (2,2 -bis(diphenylphosphino)-1,1 -binaphthyl) and DavePhos (2-Dicyclohexylphosphino-2 -(N,N-dimethylamino)biphenyl) [35], were studied, as well as Ph-JosiPhos and Cy-JosiPhos (CyPF-t Bu), which were shown to be efficient in the amination of halosubstituted heterocycles [36,37], were also tested. Other donor phosphine ligands with bulky substituents (SPhos, XPhos, RuPhos BrettPhos) were not studied in this reaction as they earlier had been shown to be much less efficient in the heteroarylation of adamantane-containing amines with 2-bromopyridines [38].…”

Section: Resultsmentioning

confidence: 99%

Mono- and Diamination of 4,6-Dichloropyrimidine, 2,6-Dichloropyrazine and 1,3-Dichloroisoquinoline with Adamantane-Containing Amines

et al. 2021

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N-heteroaryl substituted adamantane-containing amines are of substantial interest for their perspective antiviral and psychotherapeutic activities. Chlorine atom at alpha-position of N-heterocycles has been substituted by the amino group using convenient nucleophilic substitution reactions with a series of adamantylalkylamines. The prototropic equilibrium in these compounds was studied using NMR spectroscopy. The introduction of the second amino substituent in 4-amino-6-chloropyrimidine, 2-amino-chloropyrazine, and 1-amino-3-chloroisoquinoline was achieved using Pd(0) catalysis.

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Palladium‐Catalyzed Amination of Aryl Halides

Cited by 23 publications

References 264 publications

Ullmann‐Goldberg and Buchwald‐Hartwig C−N Cross Couplings: Synthetic Methods to Pharmaceutically Potential N‐Heterocycles

Ullmann‐Goldberg and Buchwald‐Hartwig C−N Cross Couplings: Synthetic Methods to Pharmaceutically Potential N‐Heterocycles

Room-Temperature Amination of Chloroheteroarenes in Water by a Recyclable Copper(II)-Phosphaadamantanium Sulfonate System

Mono- and Diamination of 4,6-Dichloropyrimidine, 2,6-Dichloropyrazine and 1,3-Dichloroisoquinoline with Adamantane-Containing Amines

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