Preparation of N-Alkyl 2-Pyridones via a Lithium Iodide Promoted O- to N-Alkyl Migration: Scope and Mechanism

Tasker, Sarah Z.; Bosscher, Michael A.; Shandro, Christina A.; Lanni, Erica L.; Ryu, Keun Ah; Snapper, Gregory S.; Utter, Jarrad M.; Ellsworth, Bruce A.; Anderson, C. L.

doi:10.1021/jo3015424

Cited by 31 publications

(14 citation statements)

References 40 publications

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“…Apparently, the trifluoromethylation was accompanied by the O – N migration of the methyl group. The O – N migration of alkoxypyridines is well documented and has been reported to be catalyzed by LiI [ 31 , 32 ], late transition metals, such as Ru and Ir [ 33 , 34 ], or TfOH [ 35 ]. It is interesting to note, though, that in the literature precedent, the O – N methyl migration in 4-methoxyquinoline requires harsher conditions [ 36 ].…”

Section: Resultsmentioning

confidence: 99%

Copper-Catalyzed Trifluoromethylation of Alkoxypyridine Derivatives

Győrfi¹,

Farkas²,

Nemet³

et al. 2020

Molecules

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The trifluoromethylation of aromatic and heteroaromatic cores has attracted considerable interest in recent years due to its pharmacological relevance. We studied the extension of a simple copper-catalyzed trifluoromethylation protocol to alkoxy-substituted iodopyridines and their benzologs. The trifluoromethylation proceeded smoothly in all cases, and the desired compounds were isolated and characterized. In the trifluoromethylation of 3-iodo-4-methoxyquinoline, we observed a concomitant O-N methyl migration, resulting in the trifluoromethylated quinolone as a product. Overall, the described procedure should facilitate the broader use of copper-catalyzed trifluoromethylation in medicinal chemistry.

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Section: Resultsmentioning

confidence: 99%

Copper-Catalyzed Trifluoromethylation of Alkoxypyridine Derivatives

Győrfi¹,

Farkas²,

Nemet³

et al. 2020

Molecules

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“…As a juxtaposition, suprafacial [1,3]-sigmatropic rearrangements are thermally disallowed 9 but Ru 10 and Ir 11 catalysts can promote formal sigmatropic [1,3]-rearrangements of 2-benzyloxypyridine derivatives at elevated temperatures (eqn (2)). 12 To our knowledge, enantioselective methods for O -to- N rearrangements yielding propargylic products have not been reported 13 and, moreover, enantioselective O -to- N [1,3]-rearrangements are extremely rare. 14 Here we report that a chiral Cu–diphosphine complex can promote the formal [1,3]-rearrangement of 2-propargyloxypyridines to enantioenriched N -propargylic-2-pyridones at temperatures as low as –40 °C (eqn (3)).…”

Section: Introductionmentioning

confidence: 99%

Enantioselective propargylic [1,3]-rearrangements: copper-catalyzed O-to-N migrations toward C–N bond formation

2017

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“…Having direct control over the light-driven formation of a highly selective final product, bypassing unnecessary experimental steps, would be beneficial for applications in portable energy conversion. For example, alkyl migration reactions are commonly used to obtain the desired products in numerous selective synthesis procedures. − Currently, there have been no reports of using plasmonic materials to initiate and carry out an alkyl migration. In this study, we examine a selective intramolecular methyl migration that is activated by introducing an organic heterocyclic amine to a strongly amplified plasmonic environment.…”

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confidence: 99%

Plasmon-Mediated Intramolecular Methyl Migration with Nanoscale Spatial Control

et al. 2020

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Plasmonic materials interact strongly with light to focus and enhance electromagnetic radiation down to nanoscale volumes. Due to this localized confinement, materials that support localized surface plasmon resonances are capable of driving energetically unfavorable chemical reactions. In certain cases, the plasmonic nanostructures are able to preferentially catalyze the formation of specific photoproducts, which offers an opportunity for the development of solar-driven chemical synthesis. Here, using plasmonic environments, we report inducing an intramolecular methyl migration reaction, forming 4-methylpyridine from N-methylpyridinium. Using both experimental and computational methods, we were able to confirm the identity of the N-methylpyridinium by making spectral comparisons against possible photoproducts. This reaction involves breaking a C–N bond and forming a new C–C bond, highlighting the ability of plasmonic materials to drive complex and selective reactions. Additionally, we observe that the product yield depends strongly on optical illumination conditions. This is likely due to steric hindrance in specific regions on the nanostructured plasmonic substrate, providing an optical handle for driving plasmonic catalysis with spatial specificity. This work adds yet another class of reactions accessible by surface plasmon excitation to the ever-growing library of plasmon-mediated chemical reactions.

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Preparation of N-Alkyl 2-Pyridones via a Lithium Iodide Promoted O- to N-Alkyl Migration: Scope and Mechanism

Cited by 31 publications

References 40 publications

Copper-Catalyzed Trifluoromethylation of Alkoxypyridine Derivatives

Copper-Catalyzed Trifluoromethylation of Alkoxypyridine Derivatives

Enantioselective propargylic [1,3]-rearrangements: copper-catalyzed O-to-N migrations toward C–N bond formation

Plasmon-Mediated Intramolecular Methyl Migration with Nanoscale Spatial Control

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