From amides to urea derivatives or carbamates with chemospecific C–C bond cleavage at room temperature

Lv, Cong; Liu, Dan; Muschin, Tegshi; Bai, Chaolumen; Bao, Agula; Bao, Yong‐Sheng

doi:10.1039/d1qo01922h

Cited by 6 publications

(10 citation statements)

References 65 publications

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“…Our previous work proved that the C−H bond oxygenation and C−C bond-oxygenated cleavage are a pair of competition processes in the [Cu]/O 2 catalytic system. 39 Aiming to eliminate the competitive C−C bond-activated product, various solvents were screened (entries 2−4). When CH 3 CN was used as a solvent, the desired product 3aa was isolated in the best selectivity (entry 4).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…2-(Naphthalen-2-yl)-2-oxo-N-(pyridin-2-yl)acetamide 7. 39 White solid; yield: 40% (M = 276.09, 11.0 mg). 1 (31.4 mg, 0.12 mmol) in HFIP (1.0 mL) was charged in a 25 mL oven-dried reaction tube under vacuum.…”

Section: N-(3-methylpyridin-2-yl)-2-(4-(trifluoromethyl)phenyl)acetam...mentioning

confidence: 99%

“…More importantly, the oxygenation reaction of general organic substrates using dioxygen as the oxygen source offers one of the most ideal processes for the construction of O-containing compounds . Pioneered by the Jiao group, the [Cu]/O 2 radical oxygenation strategy has been exploited as an excellent method in the C–C bond oxygenation cleavage of 1,3-diones, ketones, oxime acetates, and nitriles. − Recently, our laboratory proposed a combination strategy of the resonant six-membered N,O-chelation assistance and [Cu]/O 2 radical oxygenation strategy for the C–C bond oxygenation cleavage of amides . Driven by more selectivity, sustainability, and environment friendliness, we envision extending this combination strategy to the synthetic challenge of breaking the C–N bond of omnipresent secondary amides.…”

Section: Introductionmentioning

confidence: 99%

“…32−38 Recently, our laboratory proposed a combination strategy of the resonant six-membered N,Ochelation assistance and [Cu]/O 2 radical oxygenation strategy for the C−C bond oxygenation cleavage of amides. 39 Driven by more selectivity, sustainability, and environment friendliness, we envision extending this combination strategy to the synthetic challenge of breaking the C−N bond of omnipresent secondary amides.…”

Section: ■ Introductionmentioning

confidence: 99%

“…133.6, 132.9, 131.8, 128.6, 127.6, 127.6, 127.4, 127.4, 127.36, 126.0, 125.5, 123.2, 119.1, 43.4.N-(3-Methylpyridin-2-yl)-2-naphthamide 1a11 39. Yield: 80% (M = 262.11, 2.10 g) 1.…”

mentioning

confidence: 99%

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Copper-Catalyzed Transamidation of Unactivated Secondary Amides via C–H and C–N Bond Simultaneous Activations

Zhao

Wang

et al. 2023

J. Org. Chem.

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Here, we demonstrate that α-C−H and C−N bonds of unactivated secondary amides can be activated simultaneously by the copper catalyst to synthesize α-ketoamides or α-ketoesters in one step, which is a challenging and underdeveloped transformation. Using copper as a catalyst and air as an oxidant, the reaction is compatible with a broad range of acetoamides, amines, and alcohols. The preliminary mechanism studies and density functional theory calculation indicated that the reaction process may undergo first radical α-oxygenation and then transamidation with the help of the resonant six-membered N,O-chelation and molecular oxygen plays a role as an initiator to trigger the transamidation process. The combination of chelation assistance and dioxygen selective oxygenation strategy would substantially extend the modern mild synthetic amide cleavage toolbox, and we envision that this broadly applicable method will be of great interest in the biopharmaceutical industry, synthetic chemistry, and agrochemical industry.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: N-(3-methylpyridin-2-yl)-2-(4-(trifluoromethyl)phenyl)acetam...mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

“…133.6, 132.9, 131.8, 128.6, 127.6, 127.6, 127.4, 127.4, 127.36, 126.0, 125.5, 123.2, 119.1, 43.4.N-(3-Methylpyridin-2-yl)-2-naphthamide 1a11 39. Yield: 80% (M = 262.11, 2.10 g) 1.…”

mentioning

confidence: 99%

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Copper-Catalyzed Transamidation of Unactivated Secondary Amides via C–H and C–N Bond Simultaneous Activations

Zhao

Wang

et al. 2023

J. Org. Chem.

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Amine-Induced Selective C–C Bond Cleavage of 2,2,2-Trifluoroethyl Carbonyls for the Synthesis of Ureas and Amides

Mao

2023

J. Org. Chem.

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An efficient and selective transformation of 2,2,2-trifluoroethyl carbonyls into ureas/amides with amines is reported. This protocol allows the selective cleavage of the C–C bond of 2,2,2-trifluoroethyl carbonyls under transition metal-free and oxidant-free conditions, which is in contrast to the analogous C–F or C–CF3 bond functionalization. This reaction reveals the unexplored reactivity of 2,2,2-trifluoroethyl carbonyls and exhibits a broad substrate range and good functional group tolerance.

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Copper(II)-Mediated Dual Reactivity of 2-(5-Phenylisoxazol-3-yl)aniline: Directed Amination and Oxidative C(═O)─C Cleavage of Amides Enabling Direct Access to Urea Derivatives

Manna,

Khamaru,

Pathi

et al. 2024

Org. Lett.

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The dual reactivity of amides fused to 2-(5-phenylisoxazol-3-yl)aniline as a directing group for the formation of urea derivatives via chemospecific cleavage of the C(O)C bond and C(sp2)–H amination is reported here. Employing inexpensive copper as the catalyst and O2 in air as the oxidant, this protocol exhibited broad functional group tolerance for both the transformations. Detailed mechanistic studies and DFT calculations were performed to gain insights into a plausible mechanism for the formation of urea derivatives.

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From amides to urea derivatives or carbamates with chemospecific C–C bond cleavage at room temperature

Abstract: The ureas and carbamates are common motifs in pharmaceuticals, agrochemicals, biologically active compounds and organocatalysis applications. Herein, we report a significant advance in this area and present the general method...

Cited by 6 publications

References 65 publications

Copper-Catalyzed Transamidation of Unactivated Secondary Amides via C–H and C–N Bond Simultaneous Activations

Copper-Catalyzed Transamidation of Unactivated Secondary Amides via C–H and C–N Bond Simultaneous Activations

Amine-Induced Selective C–C Bond Cleavage of 2,2,2-Trifluoroethyl Carbonyls for the Synthesis of Ureas and Amides

Copper(II)-Mediated Dual Reactivity of 2-(5-Phenylisoxazol-3-yl)aniline: Directed Amination and Oxidative C(═O)─C Cleavage of Amides Enabling Direct Access to Urea Derivatives

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