Direct α-methylenation of triazines to terminal olefins with DMA

Zeng, Ming; Liu, Yixuan; Zheng, Jianbin; Zhao, Lilong; Zhu, Qi-han; Jiang, Dengzhao; Ling, Yun; Liu, Wenbo; Zeng, Shenxin

doi:10.1039/d2nj04417j

Cited by 2 publications

(4 citation statements)

References 55 publications

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“…Initially, 1a was activated by a hydrogen proton to give 1a' [24][25][26]28], which subsequently reacted with CuX2 to afford I and II [33]. Then, the reaction between II and H2O generating III and IV (IV-1 or IV-2 was formed through the reductive elimination process [14,[36][37][38]. In the presence of metal catalyst, oxygen, or sodium nitrite [39][40][41][42][43][44][45][46][47][48], IV (IV-1 or IV-2) underwen dehydrogenation to afford the desired product 2a [41,[46][47][48] (Scheme 3).…”

Section: Resultsmentioning

confidence: 99%

“…In this transformation, water participates in the reaction and offers the oxygen for the process with a palladium catalyst, producing phenyl(pyridin-2-yl)methanone in 44% yield, which inspires us to take water as an oxygen donor for an oxidation reaction in the presence of non-noble metals. More recently, our research group has reported a copper-catalyzed synthesis of aroyl triazines and terminal olefin-substituted triazines [36,37]. Surprisingly, in our attempt to obtain N 2 ,N 2 -dimethyl-N 4 -phenyl-6-(1-(pyridin-2-yl)vinyl)-1,3,5-triazine-2,4-diamine, the corresponding oxidation product was observed instead, so we proved that water can provide oxygen for the curtain oxidation transformation.…”

Section: Introductionmentioning

confidence: 99%

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Oxygen-Free Csp3-H Oxidation of Pyridin-2-yl-methanes to Pyridin-2-yl-methanones with Water by Copper Catalysis

Zeng,

Chen,

Luo

et al. 2023

Molecules

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Aromatic ketones are important pharmaceutical intermediates, especially the pyridin-2-yl-methanone motifs. Thus, synthetic methods for these compounds have gained extensive attention in the last few years. Transition metals catalyze the oxidation of Csp3-H for the synthesis of aromatic ketones, which is arresting. Here, we describe an efficient copper-catalyzed synthesis of pyridin-2-yl-methanones from pyridin-2-yl-methanes through a direct Csp3-H oxidation approach with water under mild conditions. Pyridin-2-yl-methanes with aromatic rings, such as substituted benzene, thiophene, thiazole, pyridine, and triazine, undergo the reaction well to obtain the corresponding products in moderate to good yields. Several controlled experiments are operated for the mechanism exploration, indicating that water participates in the oxidation process, and it is the single oxygen source in this transformation. The current work provides new insights for water-involving oxidation reactions.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Oxygen-Free Csp3-H Oxidation of Pyridin-2-yl-methanes to Pyridin-2-yl-methanones with Water by Copper Catalysis

Zeng,

Chen,

Luo

et al. 2023

Molecules

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“…The initial compound 1 was prepared as referred to in our previous work [38,39,45]. Sodium (2.5 eq) was added to anhydrous MeOH at 0 • C until the sodium was completely consumed.…”

Section: General Procedures For the Synthesis Ofmentioning

confidence: 99%

“…More recently, Cui and their group reported the efficient copper-catalyzed sulfonamidation of arenes via C-H activation, with triazine as the directing group [34]. Inspired by our previous work [35][36][37][38][39], we reasoned that N-aryl-triazines are suitable substrates for the synthesis of indole-substituted triazines through C-H activation. We herein describe the ruthenium-catalyzed synthesis of N-triazine-substituted indoles from N-aryl-triazines and alkynes.…”

Section: Introductionmentioning

confidence: 96%

Ruthenium-Catalyzed Oxidative Synthesis of N-(2-triazine)indoles by C-H Activation

et al. 2023

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1,3,5 triazines, especially indole functionalized triazine derivatives, exhibit excellent activities, such as anti-tumor, antibacterial, and anti-inflammatory activities. Traditional methods for the synthesis of N-(2-triazine) indoles suffer from unstable materials and tedious operations. Transition-metal-catalyzed C-C/C-N coupling provides a powerful protocol for the synthesis of indoles by the C-H activation strategy. Here, we report the efficient ruthenium-catalyzed oxidative synthesis of N-(2-triazine) indoles by C-H activation from alkynes and various substituted triazine derivatives in a moderate to good yield, and all of the N-(2-triazine) indoles were characterized by 1H NMR, 13C NMR, and HRMS. This protocol can apply to the gram-scale synthesis of the N-(2-triazine) indole in a moderate yield. Moreover, the reaction is proposed to be performed via a six-membered ruthenacycle (II) intermediate, which suggests that the triazine ring could offer chelation assistance for the formation of N-(2-triazine) indoles.

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Direct α-methylenation of triazines to terminal olefins with DMA

Abstract: We report an efficient metal (Cu or Ni) -catalysed α‑Methylenation of triazines to terminal olefins using DMA as one carbon source. Various substituted triazine derivatives are suitable for this reaction.

Cited by 2 publications

References 55 publications

Oxygen-Free Csp3-H Oxidation of Pyridin-2-yl-methanes to Pyridin-2-yl-methanones with Water by Copper Catalysis

Oxygen-Free Csp3-H Oxidation of Pyridin-2-yl-methanes to Pyridin-2-yl-methanones with Water by Copper Catalysis

Ruthenium-Catalyzed Oxidative Synthesis of N-(2-triazine)indoles by C-H Activation

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