Heterogeneous manganese-oxide-catalyzed successive cleavage and functionalization of alcohols to access amides and nitriles

He, Peipei; Chen, Bin; Huang, Liang; Liu, Xixi; Qin, Jingzhong; Zhang, Zehui; Dai, Wen

doi:10.1016/j.chempr.2022.02.021

Cited by 24 publications

(27 citation statements)

References 57 publications

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“…Based on these experimental data and previous reports, , a plausible mechanistic pathway is proposed as depicted in Scheme . First, a superoxide radical is generated by single-electron transfer from Cu(I) to O 2 .…”

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confidence: 67%

“…In continuation of our long-time interest in the value-added transformation of chemical feedstocks via cleavage and functionalization of C–C bonds, we explored the further application of this strategy for cyanation of multicarbon alkyl-substituted (hetero)arenes to access aryl nitriles. Copper salts, owing to their unique properties such as multiple oxidation states, high abundancy, and low toxicity, play an indispensable role in the catalysis field .…”

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confidence: 99%

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Copper-Catalyzed Oxidative C–C Bond Cleavage of Alkyl-(Hetero)arenes Enabling Direct Access to Nitriles

et al. 2022

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The cleavage and functionalization of C−C bonds has emerged as a powerful tool for discovery of new transformations. Herein, we report a protocol that enables direct synthesis of nitriles via copper-catalyzed oxidative cleavage and cyanation of C−C bonds in a wide variety of multicarbon alkyl-substituted (hetero)arenes. Detailed mechanistic studies reveal that a tandem oxidative process is involved in this transformation.

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confidence: 67%

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confidence: 99%

Copper-Catalyzed Oxidative C–C Bond Cleavage of Alkyl-(Hetero)arenes Enabling Direct Access to Nitriles

et al. 2022

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“…10 Very recently, our group has developed a procedure for the synthesis of (hetero)aromatic primary amides via successive cleavage and ammoxidation of alcohols under heterogeneous amorphous manganese oxide catalysis. 11 In this method, a range of primary and secondary alcohols can be transformed into one- or multiple-carbon shorter amides smoothly. Although our heterogeneous catalyst is chemistry and air-stable, recyclable, reusable, low-cost, low-toxicity, and easily prepared, the protocols for its preparation may not be applicable to the entire spectrum of scientific communities.…”

Section: Table 1 Optimization Of the Reaction Condition...mentioning

confidence: 99%

“…As part of our long-time interest in value-added transformation of chemical feedstocks via cleavage and functionalization of C–C bonds, 11 12 13 14 15 we intend to further explore the application of this strategy for amidation of primary and secondary alcohols. Similar to manganese oxides, manganese salts play an indispensable role in the oxidation catalysis field owing to their unique properties such as multiple oxidation states, high abundance, and low toxicity.…”

Section: Table 1 Optimization Of the Reaction Condition...mentioning

confidence: 99%

A Mn(II)-Catalyzed Tandem Oxidative Cleavage and Ammoxidation of Alcohols to Primary Amides

Zhao

Xie

et al. 2023

Synlett

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The cleavage/functionalization of C-C bonds in alcohols has emerged as a robust tool for exploration of new conversion. Herein, a Mn(OAc)2-catalyzed oxidative cleavage/ammoxidation of a wide range of alcohols to amides has been developed. The practicality of this transformation was demonstrated by a scale-up experiment and an amidation of mixed alcohols in a one-pot fashion. Moreover, a plausible mechanism was proposed based on a series of control experiments.

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“… 23 Taking together, we envisioned that manganese oxides might be potential candidates for tandem oxidative cleavage and ammoxidation of C=C double bonds in alkenes. As part of our continued interest in value-added transformation of chemical feedstocks, 24 , 25 herein, for the first time, we report a manganese oxide-catalyzed tandem oxidative cleavage/ammoxidation that enables direct synthesis of amides from unsaturated hydrocarbons ( Figure 1 c). A diverse set of mono- and multisubstituted aromatic and aliphatic alkenes or alkynes are smoothly converted into amides with O 2 as an oxidant and NH 3 as a nitrogen source.…”

Section: Introductionmentioning

confidence: 99%

Oxidative Cleavage and Ammoxidation of Unsaturated Hydrocarbons via Heterogeneous Auto-Tandem Catalysis

Chen

Zhang

Luo

et al. 2023

JACS Au

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The oxidative cleavage and functionalization of unsaturated C–C bonds are important processes for synthesis of carbonyl compounds from hydrocarbon feedstocks, yet there has been no report of direct amidation of unsaturated hydrocarbons via an oxidative cleavage of unsaturated C–C bonds with molecular oxygen as an environmentally benign oxidant. Herein, for the first time, we describe a manganese oxide-catalyzed auto-tandem catalysis strategy that enables direct synthesis of amides from unsaturated hydrocarbons by coupling oxidative cleavage with amidation. With oxygen as an oxidant and ammonia as a nitrogen source, a wide range of structurally diverse mono- and multisubstituted activated and unactivated alkenes or alkynes can smoothly undergo unsaturated C–C bond cleavage to deliver one- or multiple-carbon shorter amides. Moreover, a slight modification of the reaction conditions also allows for the direct synthesis of sterically hindered nitriles from alkenes or alkynes. This protocol features excellent functional group tolerance, a broad substrate scope, flexible late-stage functionalization, facile scalability, and a cost-effective and recyclable catalyst. Detailed characterizations reveal that the high activity and selectivity of the manganese oxides are attributed to the large specific surface area, abundant oxygen vacancies, better reducibility, and moderate acid sites. Mechanistic studies and density functional theory calculations indicate that the reaction proceeds through divergent pathways depending on the structure of substrates.

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Heterogeneous manganese-oxide-catalyzed successive cleavage and functionalization of alcohols to access amides and nitriles

Cited by 24 publications

References 57 publications

Copper-Catalyzed Oxidative C–C Bond Cleavage of Alkyl-(Hetero)arenes Enabling Direct Access to Nitriles

Copper-Catalyzed Oxidative C–C Bond Cleavage of Alkyl-(Hetero)arenes Enabling Direct Access to Nitriles

A Mn(II)-Catalyzed Tandem Oxidative Cleavage and Ammoxidation of Alcohols to Primary Amides

Oxidative Cleavage and Ammoxidation of Unsaturated Hydrocarbons via Heterogeneous Auto-Tandem Catalysis

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