Palladium-Catalyzed C,N-Cross Coupling Reactions of 3<i>-</i>Halo-2-aminopyridines

Perez, Felix; Minatti, Ana

doi:10.1021/ol200371n

Cited by 25 publications

(12 citation statements)

References 26 publications

(20 reference statements)

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“…However, the difference in catalytic activity between two kinds of widely used catalyst ligands, BrettPhos and RuPhos, − has not been understood well. As shown in Figure b, the following question arises: why does BrettPhos have high catalytic activity for primary amines, while RuPhos has high catalytic activity for secondary amines?…”

Section: Introductionmentioning

confidence: 99%

Ligand Effects of BrettPhos and RuPhos on Rate-Limiting Steps in Buchwald–Hartwig Amination Reaction Due to the Modulation of Steric Hindrance and Electronic Structure

Tian

Wang

et al. 2020

ACS Omega

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The differences in catalytic activity between two catalyst ligands of Buchwald–Hartwig amination reaction, BrettPhos versus RuPhos, were investigated using density functional theory (DFT) calculations. The reaction process consists of three consecutive steps: (1) oxidative addition, (2) deprotonation, and (3) reductive elimination. Among them, the rate-limiting step of Pd-BrettPhos catalytic system is oxidative addition but that of Pd-RuPhos catalytic system is reductive elimination due to their differences in steric hindrance and electronic structure. It was also revealed that amines with large-size substituents or halides with electron-withdrawing groups would reduce the activation energy barriers of the reactions. The insights gained from the calculations of the Buchwald–Hartwig amination reaction would be helpful for the rational designing of new catalysts and reactions.

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Section: Introductionmentioning

confidence: 99%

Ligand Effects of BrettPhos and RuPhos on Rate-Limiting Steps in Buchwald–Hartwig Amination Reaction Due to the Modulation of Steric Hindrance and Electronic Structure

Tian

Wang

et al. 2020

ACS Omega

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“…Ageneral advantage of this methylation of nitroarenes is the feasibility to simply combine it with well-established coupling processes [17,18,20] using the same molecularly-defined catalyst. To demonstrate this concept, the selected N-methylarylamines were further functionalized to av ariety of coupling products (Scheme 5).…”

Section: Zuschriftenmentioning

confidence: 99%

“…[15,16] Here,the activation of the corresponding alcohol is facilitated by the Na tom of the pyridyl ring. Hence,this ligand motif should be also beneficial in hydrogen transfer reactions.T herefore,wehad the idea to synthesize new bifunctional ligands,w hich combine the advantages of LB and state-of-the-art sterically hindered (hetero)arylphosphines such as Buchwald ligands [17] or our previously reported imidazole-substituted monophosphines LC [18] (Scheme 2a).…”

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confidence: 99%

Palladium‐Catalyzed Methylation of Nitroarenes with Methanol

2019

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Ap rocedure for the synthesis of N-methyl-arylamines directly from nitroarenes using methanol as green methylating agent was developed. The key to success is the use of aspecific catalyst system consisting of palladium acetate and the ligand 1-[2,6-bis(isopropyl)phenyl]-2-[tert-butyl(2-pyridinyl)phosphino]-1H-Imidazole (L1). The generality of this protocol is demonstrated in the synthesis of more than 20 Nmethyl-arylamines under comparably mild conditions.C ombining this novel methodology with subsequent coupling processes using the same catalyst allows for efficient diversification of aromatic nitro compounds to ab road variety of amines including drug molecules. Scheme 1. Representative examples of drugs containing N-methylamines. Scheme 2. a) Ligand design for Pd-catalyzeds ynthesis of N-methylarylamines. b) Potential further functionalization.

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“…Transition‐metal‐catalyzed reaction is always the main force in cross‐coupling reactions, which plays an important role in the formation of C‐N bonds and C‐heteroatom bonds . Especially, the N ‐aryl nitrogen heterocycle motif is present in a multitude of bioactive natural products and pharmaceutically interesting compounds, such as the Gleevec and Osimertinb potent anticancer drug (Figure ) .…”

Section: Introductionmentioning

confidence: 99%

The palladium‐catalyzed C‐N cross‐coupling reaction of diheteroaryl disulfides with heterocyclic amines

Liu

Zhang

Quan

et al. 2017

Applied Organom Chemis

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The Pd‐catalyzed cross‐coupling reaction of 1, 2‐di(pyrimidin‐2‐yl) disulfides with heterocyclic amines including 2‐amino pyrimidines and 1,3,4‐thiadiazol‐2‐amines to deliver symmetrical C‐N coupling products in moderate to good yields is reported. This method provides an opportunity for synthesis of bioactive molecules and pharmaceutically interesting compounds containing heterocycle motifs. The reported protocol shows good functional group compatibility, and provides a new strategy for preparation of C2‐amination pyrimidine derivatives from heterocyclic disulfides.

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Palladium-Catalyzed C,N-Cross Coupling Reactions of 3-Halo-2-aminopyridines

Cited by 25 publications

References 26 publications

Ligand Effects of BrettPhos and RuPhos on Rate-Limiting Steps in Buchwald–Hartwig Amination Reaction Due to the Modulation of Steric Hindrance and Electronic Structure

Ligand Effects of BrettPhos and RuPhos on Rate-Limiting Steps in Buchwald–Hartwig Amination Reaction Due to the Modulation of Steric Hindrance and Electronic Structure

Palladium‐Catalyzed Methylation of Nitroarenes with Methanol

The palladium‐catalyzed C‐N cross‐coupling reaction of diheteroaryl disulfides with heterocyclic amines

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