Carbon Nanofibrous Microspheres Promote the Oxidative Double Carbonylation of Alkanes with CO

Lu, Lijun; Pei, Xianglin; Mei, Yuan; Deng, Yi; Zhang, Heng; Zhang, Lina; Lei, Aiwen

doi:10.1016/j.chempr.2018.09.003

Cited by 26 publications

(17 citation statements)

References 59 publications

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“…Based on the above experimental evidences and previous literatures, [18,19,21] a plausible mechanism for this Mn(III)‐promoted double carbonylation toward the synthesis of α ‐ketoamides is proposed (Scheme 4). Firstly, alkyltrifluoroborate undergoes a single electron transfer (SET) process by Mn(III) to produce the alkyl radical.…”

Section: Methodsmentioning

confidence: 60%

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Manganese(III)‐Promoted Double Carbonylation of Anilines Toward α‐Ketoamides Synthesis

Chen

Kuai

et al. 2021

Adv Synth Catal

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Employing anilines as nucleophiles in double carbonylation is a longstanding challenge. In this communication, a Mn(III)‐promoted double carbonylation of alkylborates or Hantzsch esters with anilines toward the synthesis of α‐ketoamides has been developed. By using easily available potassium alkyltrifluoroborates or Hantzsch esters as the starting material, and cheap and non‐toxic Mn(OAc)3 ⋅ 2H2O as the promotor, a broad range of alkyl α‐ketoamide derivatives were synthesized in moderate to good yields with excellent selectivity.

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Section: Methodsmentioning

confidence: 60%

“…Due to the decreased basicity, anilines were usually failed in double carbonylation chemistry. Recently, Lu et al reported an interesting oxidative double carbonylation of symmetric alkanes for the preparation of α‐ketoamides [18] . In this procedure, anilines were applied successfully with alkenes as the substrates and solvents.…”

Section: Methodsmentioning

confidence: 99%

Manganese(III)‐Promoted Double Carbonylation of Anilines Toward α‐Ketoamides Synthesis

Chen

Kuai

et al. 2021

Adv Synth Catal

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“…Subsequently, a number of organic azides were examined. Benzenesulfonyl azides bearing an electron-donating group (OMe) or a halogen atom (F, Cl, Br, I) were well tolerated in this reaction (26)(27)(28)(29)(30). In addition, the expected products 32-38 were also obtained in good yields from hetaryl and alkylsulfonyl azides.…”

Section: Scheme 3 Our Initial Hypothesis Regarding C-h Amidation Withmentioning

confidence: 97%

“…Recently, oxidative C-H aminocarbonylation of cycloalkanes promoted by carbon nanofibrous microspheres with DTBP as the oxidant was achieved by Zhang, Lei and coworkers. 27 Notably, two CO moieties were introduced, generating -carbonyl amides as the products.…”

Section: Synpacts Synlettmentioning

confidence: 99%

Transition-Metal-Catalyzed Intermolecular C–H Carbonylation toward Amides

Liu

Xia

2020

Synlett

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The amide linkage is one of the most important structural moieties in both chemistry and biology. Here, we briefly discuss recent advances in catalytic intermolecular C–H carbonylation reactions for the synthesis of amides, with particular attention to our intermolecular C–H amidation of arenes with carbon monoxide and organic azides to produce amides.1 Introduction2 Representative Methods for Amide Synthesis3 C–H Aminocarbonylation with Carbon Monoxide and Amines4 C–H Amidation to Amides with Carbon Monoxide and Azides5 Summary and Outlook

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“…10 Building on the special adsorbability of chitin-derived carbon nanofibrous microspheres (CNMs), Lei and Zhang reported a breakthrough method of employing CNMs as a promoter to realize an oxidative double radical carbonylation of alkanes for synthesis of various alkyl α-ketoamides using stoichiometric di-tert-butyl peroxide (DTBP) as oxidant. 11 In addition to these inspiring studies, numerous other catalytic methods for single or double carbonylation reactions proceeding via ionic or radical pathways have also been reported and extensively studied. [12][13][14][15][16] However, to our knowledge, a generally applicable catalytic system that allowed controlled switchable single and double carbonylative formation of value-added products from the same and simple starting materials is still unknown.…”

mentioning

confidence: 99%

Switchable radical carbonylation by polarity-regulation

Lü

Xiao

et al. 2021

Preprint

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Carbonylation reactions involving CO as readily available C1 synthons have become one of the most important tools for construction of carbonyl compounds from feedstock chemicals in modern chemical synthesis. Whereas numerous catalytic methods for carbonylation reactions proceeding via ionic or radical pathways have been reported, an inherent limitation to these methods is the need to control switchable single and double carbonylative formation of value-added products from the same and simple starting materials. Here we describe a new strategy that exploits simple visible-light-driven photoredox catalysis to regulate the polarity of coupling partners to drive switchable radical carbonylation reactions. Controlled trap of various alkyl radicals by single or double CO thereby proceed smoothly with excellent selectivity in the presence of various amine nucleophiles at room temperature, generating valuable amides and α-ketoamides in a versatile and controlled fashion. Combined experimental and DFT computational studies suggest that trap of the initially formed acyl radical by the second molecule of CO to form α-ketoacyl radical is a facile but reversible process; and photoredox-catalyzed SET oxidation of natural nucleophilic amines into relatively electrophilic nitrogen radical cations is responsible for switchable coupling with such two radical intermediates.

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Carbon Nanofibrous Microspheres Promote the Oxidative Double Carbonylation of Alkanes with CO

Cited by 26 publications

References 59 publications

Manganese(III)‐Promoted Double Carbonylation of Anilines Toward α‐Ketoamides Synthesis

Manganese(III)‐Promoted Double Carbonylation of Anilines Toward α‐Ketoamides Synthesis

Transition-Metal-Catalyzed Intermolecular C–H Carbonylation toward Amides

Switchable radical carbonylation by polarity-regulation

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