Oxidative N‐Heterocyclic Carbene‐Catalyzed γ‐Carbon Addition of Enals to Imines: Mechanistic Studies and Access to Antimicrobial Compounds

Zheng, Pengcheng; Cheng, Jiajia; Su, Shihu; Jin, Zhichao; Wang, Yu‐Huang; Yang, Song; Jin, Linhong; Song, Baoan; Robin, Yonggui

doi:10.1002/chem.201501632

Cited by 41 publications

(15 citation statements)

References 80 publications

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“…Examples of such molecules include natural product Epicocconigrone A with anticancer activities44 and Efavirenz, commercially used as an HIV reverse transcriptase inhibitor45. Our laboratories are interested in the antiviral and antibacterial activities of these compounds for agricultural use464748. Therefore, we then evaluated the in vitro bioactivities of our products against several types of bacteria and fungi that can cause plant infections (Table 4).…”

Section: Resultsmentioning

confidence: 99%

A reaction mode of carbene-catalysed aryl aldehyde activation and induced phenol OH functionalization

et al. 2017

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The research in the field of asymmetric carbene organic catalysis has primarily focused on the activation of carbon atoms in non-aromatic scaffolds. Here we report a reaction mode of carbene catalysis that allows for aromatic aldehyde activation and remote oxygen atom functionalization. The addition of a carbene catalyst to the aldehyde moiety of 2-hydroxyl aryl aldehyde eventually enables dearomatization and remote OH activation. The catalytic process generates a type of carbene-derived intermediate with an oxygen atom as the reactive centre. Inexpensive achiral urea co-catalyst works cooperatively with the carbene catalyst, leading to consistent enhancement of the reaction enantioselectivity. Given the wide presence of aromatic moieties and heteroatoms in natural products and synthetic functional molecules, we expect our reaction mode to significantly expand the power of carbene catalysis in asymmetric chemical synthesis.

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Section: Resultsmentioning

confidence: 99%

A reaction mode of carbene-catalysed aryl aldehyde activation and induced phenol OH functionalization

et al. 2017

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“…Likewise Chi and co‐workers developed a protocol for the synthesis of highly enantioselective tricyclic sulfonyl amides 91 by the γ ‐carbon addition of enal 89 to sulfonyl imine 90 under oxidative N‐heterocyclic carbene catalysis with quinone DQ as an external oxidant and the mechanism of the reaction was studied in detail (Scheme 24). [50] Based on the kinetic studies, the authors have found out that the reaction shows Zero‐order dependence on oxidant, signifying that the oxidation of Breslow intermediate to α , β ‐unsaturated acyl azolium was facile step. With respect to the catalyst, the order was found to be partial which can be ascribed to the inhibitory action of imine on the catalyst.…”

Section: Figurementioning

confidence: 99%

Recent Advances in N‐Heterocyclic Carbene Catalyzed Oxidative Cyclization for the Formation of Heterocycles

2021

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Oxidative N‐heterocyclic carbene catalyst mediated cyclization proved to be an efficient strategy for the construction of various N‐ and O‐ heterocycles. Among several metal‐free methods available for the construction of heterocyclic compounds, oxidative NHC catalysis proved to be an elegant and efficient strategy as several enantioenriched compounds with excellent enantioselectivities can be synthesized in good yields. The most common method of the generation of these heterocycles proceeds via the commonly encountered intermediate in oxidative NHC catalysis (i. e.) acyl azolium intermediate. This intermediate proves to be the active species as it can undergo reaction with suitable substrates leading to the formation of numerous N‐ and O‐ heterocycles. Herein, recent reports on different strategies that enable formal [2+2], [3+2], [3+3], [4+2] or [4+3] annulations between the incoming substrates and acyl azolium species or other active intermediates which can add to suitable substrate leading to various heterocycles were summarized.

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“…The reaction between enals 45 and imines 2b under the catalysis of NHC precatalyst Cat. 15 with quinone 50 as an external oxidant was chosen as a good model reaction for a mechanistic study of the oxidative carbene catalysis for enal γ‐carbon functionalization by Chi et al . This reaction was found to be relatively clean and easy to monitor by conventional analytical methods and provided a quick access to enantioenriched tricyclic sulfonyl amides 51 that showed promising antibacterial activities (Scheme ).…”

Section: Use Of Cyclic Imines 2 Bearing a 1h‐isoindole Moietymentioning

confidence: 99%

Organocatalytic Asymmetric Transformations Involving the Cyclic Imine Moiety in Indole and Isoindole Related Heterocycles

Cheng

Shao

2018

Adv Synth Catal

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Scheme 8. Asymmetric Mannichr eaction of 2-aryl-3H-indol-3-ones 1c with aldehydes and ketones catalyzed by l-proline. Scheme 12. Catalytic asymmetric aza-DAr eaction of 2-aryl-3H-indol-3-ones 1c with 2,4-dienals 34 via trienaminec atalysis. Scheme 18. Enantioselective[ 4 + +2] cycloaddition of ketimines 2a or 2b with allenoate 53a catalyzed by (R)-SITCP Cat. 18. Scheme 34. Bifunctional phosphine Cat. 31-catalyzed stepwise [4+ +2]/[2+ +2] cycloadditions between allene ketones 96 and 2d.

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Oxidative N‐Heterocyclic Carbene‐Catalyzed γ‐Carbon Addition of Enals to Imines: Mechanistic Studies and Access to Antimicrobial Compounds

Cited by 41 publications

References 80 publications

A reaction mode of carbene-catalysed aryl aldehyde activation and induced phenol OH functionalization

A reaction mode of carbene-catalysed aryl aldehyde activation and induced phenol OH functionalization

Recent Advances in N‐Heterocyclic Carbene Catalyzed Oxidative Cyclization for the Formation of Heterocycles

Organocatalytic Asymmetric Transformations Involving the Cyclic Imine Moiety in Indole and Isoindole Related Heterocycles

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