Regioselectivity of aminomethylation in 3-acetyl-7-hydroxycoumarins: Mannich bases and Betti bases

Gao, Fan; Deng, Tao; Ju, Cheng; Yang, Baofeng; Bao, Xiaoyong; Zhang, Dan; Zhang, Tiantai; Li, Li

doi:10.1039/d1nj01584b

Cited by 8 publications

(3 citation statements)

References 59 publications

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“…MBs as an important intermediate or product have been widely used in many fields, especially in pharmaceutical and chemical industries. 48 Thus, it is necessary to figure out the decomposition mechanism of MBs and the catalysis of ILs in this step.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Mild Catalytic Mechanism of the Mannich Reaction for Synthesizing Methylacrolein by sec-Amine Short-Chain Aliphatic Acid Ionic Liquid Catalysts

Yan

Huo

et al. 2022

ACS Sustainable Chem. Eng.

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By density functional theory (DFT), we report a detailed mechanistic study on the synthesis of methylacrolein (MAL) by a mild Mannich reaction of formaldehyde (FA) and propionaldehyde (PA) catalyzed by sec-amine short-chain aliphatic acid ionic liquids (ILs). ILs exhibit excellent catalytic activity and create mild reaction conditions (45 °C) by dramatically decreasing the reaction energy barrier (24.43 kcal mol −1 ) in the decomposition step of Mannich bases (MBs) comapred to without ILs. Three key intermediates observed by DFT calcutations were identified by electron spray ionization mass spectrometry (ESI-MS) analysis. We systematically investigated the catalytic effect of ILs with different sec-amines (HNR 2 , R = CH 3 , C 2 H 5 , etc.) on the activation energy and different short-chain aliphatic acids (RCOOH, R= H, CH 3 et al.) on the decomposition step of MBs. This work is intended to provide a thorough explanation of the synthesis mechanism of the mild Mannich reaction of MAL catalyzed by ILs from the theoretical aspect, which may give a favorable guidance for the practical application.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Mild Catalytic Mechanism of the Mannich Reaction for Synthesizing Methylacrolein by sec-Amine Short-Chain Aliphatic Acid Ionic Liquid Catalysts

Yan

Huo

et al. 2022

ACS Sustainable Chem. Eng.

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“…It has been claimed that umbelliferone may delay the progression of diabetic nephropathy, possibly by activating the Nrf2/heme-oxygenase-1 pathway, thereby reducing the level of high glucose-induced ferroptosis [38]. Additionally, in 2021, Gao et al used the Knoevenagel reaction and Pechmann condensation to develop a new series of 3-acetyl-7-hydroxycoumarin Mannich bases (3) and Betti bases (4) (Figure 3) that were explored in vitro for their anti-inflammatory activity [35]. The obtained results showed that the Mannich bases (3) possess much stronger anti-inflammatory properties than the corresponding Betti bases (4) in both the NO release and TNF-α production models.…”

Section: Antioxidant Properties Of Umbelliferonementioning

confidence: 99%

“…The obtained results showed that the Mannich bases (3) possess much stronger anti-inflammatory properties than the corresponding Betti bases (4) in both the NO release and TNF-α production models. Moreover, the structure-activity relationship analysis (SAR) revealed that the presence of the diethylamino group is beneficial to the anti-inflammatory activity [35].…”

Section: Antioxidant Properties Of Umbelliferonementioning

confidence: 99%

Umbelliferone and Its Synthetic Derivatives as Suitable Molecules for the Development of Agents with Biological Activities: A Review of Their Pharmacological and Therapeutic Potential

Kornicka,

Balewski,

Lahutta

et al. 2023

Pharmaceuticals

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Umbelliferone (UMB), known as 7-hydroxycoumarin, hydrangine, or skimmetine, is a naturally occurring coumarin in the plant kingdom, mainly from the Umbelliferae family that possesses a wide variety of pharmacological properties. In addition, the use of nanoparticles containing umbelliferone may improve anti-inflammatory or anticancer therapy. Also, its derivatives are endowed with great potential for therapeutic applications due to their broad spectrum of biological activities such as anti-inflammatory, antioxidant, neuroprotective, antipsychotic, antiepileptic, antidiabetic, antimicrobial, antiviral, and antiproliferative effects. Moreover, 7-hydroxycoumarin ligands have been implemented to develop 7-hydroxycoumarin-based metal complexes with improved pharmacological activity. Besides therapeutic applications, umbelliferone analogues have been designed as fluorescent probes for the detection of biologically important species, such as enzymes, lysosomes, and endosomes, or for monitoring cell processes and protein functions as well various diseases caused by an excess of hydrogen peroxide. Furthermore, 7-hydroxy-based chemosensors may serve as a highly selective tool for Al3+ and Hg2+ detection in biological systems. This review is devoted to a summary of the research on umbelliferone and its synthetic derivatives in terms of biological and pharmaceutical properties, especially those reported in the literature during the period of 2017–2023. Future potential applications of umbelliferone and its synthetic derivatives are presented.

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Catalyst‐Free Accelerated Three‐Component Synthesis of Betti Bases in Microdroplets

Jin

Dai

et al. 2022

ChemPlusChem

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Due to their important roles in medicine and asymmetric metal catalysis, the formation of Betti bases has attracted wide interest in organic chemical community. Traditional multicomponent reaction methods for synthesizing Betti bases normally require long reaction times under harsh conditions (high temperature, microwave or ultrasonic irradiation, etc.) in the presence of various catalysts. In this study, we developed a mild, highly efficient and environmentally friendly method to synthesize Betti bases without the use of any catalysts in microdroplets. The Betti reaction was accelerated by 6.53×103 in microdroplets by comparing the measured rate constant in bulk. Fifteen Betti bases were synthesized by the microdroplet method using a variety of aldehydes, naphthols and amines with 68–98 % yields at a scaled‐up amount of 1.9 g h−1. Overall it is an attractive alternative to classic organic synthesis for the construction of Betti bases and derivatives.

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Regioselectivity of aminomethylation in 3-acetyl-7-hydroxycoumarins: Mannich bases and Betti bases

Abstract: 7-Hydroxycoumarin is a privileged structure for anti-inﬂammatory drug development. In this study, several new 3-acetyl-7-hydroxycoumarin derivatives were designed, synthesized and tested as anti-inflammatory agents. Interestingly, Mannich bases and Betti bases...

Cited by 8 publications

References 59 publications

Mild Catalytic Mechanism of the Mannich Reaction for Synthesizing Methylacrolein by sec-Amine Short-Chain Aliphatic Acid Ionic Liquid Catalysts

Mild Catalytic Mechanism of the Mannich Reaction for Synthesizing Methylacrolein by sec-Amine Short-Chain Aliphatic Acid Ionic Liquid Catalysts

Umbelliferone and Its Synthetic Derivatives as Suitable Molecules for the Development of Agents with Biological Activities: A Review of Their Pharmacological and Therapeutic Potential

Catalyst‐Free Accelerated Three‐Component Synthesis of Betti Bases in Microdroplets

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