Copper-Catalyzed Synthesis of Coumarins. A Mini-Review

Coumarin (2H-chromen-2-one) derivatives have important uses in medicinal and synthetic chemistry, for example, as fluorescent probes. These properties have prompted chemists to develop efficient synthetic methods to synthesize the coumarin core and/or to functionalize it. In this context, many metal-catalyzed syntheses of coumarins have been introduced; among them, copper-catalyzed reactions appear to be very promising owing to the non-toxicity and cheapness of copper complexes. In this mini-review, the results in this field are summarized. We hope to stimulate other applications of these complexes in the preparation of coumarin derivatives.

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Synthetic chemistry with nitrous oxide

Chemical Society Reviews ◽

10.1039/c5cs00339c ◽

2015 ◽

Vol 44 (17) ◽

pp. 6375-6386 ◽

Cited By ~ 63

Author(s):

Kay Severin

Keyword(s):

Inorganic Chemistry ◽

Nitrous Oxide ◽

Synthetic Chemistry ◽

Laughing Gas ◽

Catalyzed Reactions ◽

Metal Catalyzed

Nitrous oxide (N2O, ‘laughing gas’) is a very inert molecule. Still, it can be used as a reagent in synthetic organic and inorganic chemistry, serving as O-atom donor, as N-atom donor, or as a oxidant in metal-catalyzed reactions.

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Transition metal-catalyzed synthesis of new 3-substituted coumarin derivatives as antibacterial and cytostatic agents

Future Medicinal Chemistry ◽

10.4155/fmc-2021-0161 ◽

2021 ◽

Author(s):

Ivana Sokol ◽

Mateja Toma ◽

Mia Krnić ◽

Andrijana Meščić Macan ◽

Domagoj Drenjančević ◽

...

Keyword(s):

Transition Metal ◽

Coumarin Derivative ◽

Carcinoma Cells ◽

Coumarin Derivatives ◽

Antitumor Potential ◽

Resistant Strains ◽

Transition Metal Catalyzed ◽

Catalyzed Reactions ◽

Metal Catalyzed ◽

Coumarin Ring

Aim: The aim of this study was to synthesize new coumarin-based compounds and evaluate their antibacterial and antitumor potential. Results: Using transition metal-catalyzed reactions, a series of 7-hydroxycoumarin derivatives were synthesized with aliphatic and aryl moiety attached directly at C-3 of the coumarin ring and through the ethynyl or 1,2,3-triazole linker. The 3-substituted coumarin derivative bearing bistrifluoromethylphenyl at the C-4 position of 1,2,3-triazole (33) showed strong and selective antiproliferative activity against cervical carcinoma cells. The 7-hydroxy-4-methylcoumarin with a phenyl ring directly attached to coumarin at C-3 (10) showed good potency against the methicillin-resistant Staphylococcus aureus and vancomycin-resistant strains. Conclusion: The most active coumarin derivatives owe their antiproliferative potential to the 3,5-ditrifluoromethylphenyl substituent (in 33) and antibacterial activity to the aromatic moiety (in 10); their structure can be optimized further for improved effect.

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Asymmetric organocatalyzed synthesis of coumarin derivatives

Beilstein Journal of Organic Chemistry ◽

10.3762/bjoc.17.128 ◽

2021 ◽

Vol 17 ◽

pp. 1952-1980

Author(s):

Natália Menezes Moreira ◽

Lorena Suelen Ribeiro Martelli ◽

Arlene Gonçalves Corrêa

Keyword(s):

Synthetic Methods ◽

Synthetic Chemistry ◽

Coumarin Derivatives

Coumarin derivatives are essential scaffolds in medicinal and synthetic chemistry. Compounds of this class have shown important activities, such as anticancer and antiparasitic, besides the commercially available drugs. These properties led to the development of efficient and greener synthetic methods to achieve the 2H-chromen-2-one core. In this context, the advances in asymmetric organocatalyzed synthesis of coumarin derivatives are discussed in this review, according to the mode of activation of the catalyst.

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Monodentate Trialkylphosphines: Privileged Ligands in Metal-catalyzed Crosscoupling Reactions

Current Organic Chemistry ◽

10.2174/1385272824666200211114540 ◽

2020 ◽

Vol 24 (3) ◽

pp. 231-264 ◽

Cited By ~ 3

Author(s):

Kevin H. Shaughnessy

Keyword(s):

Transition Metal ◽

Cross Coupling ◽

Coupling Reactions ◽

Cross Coupling Reactions ◽

Aryl Bromides ◽

Wide Range ◽

Sterically Demanding ◽

Transition Metal Catalyzed ◽

Catalyzed Reactions ◽

Metal Catalyzed

Phosphines are widely used ligands in transition metal-catalyzed reactions. Arylphosphines, such as triphenylphosphine, were among the first phosphines to show broad utility in catalysis. Beginning in the late 1990s, sterically demanding and electronrich trialkylphosphines began to receive attention as supporting ligands. These ligands were found to be particularly effective at promoting oxidative addition in cross-coupling of aryl halides. With electron-rich, sterically demanding ligands, such as tri-tertbutylphosphine, coupling of aryl bromides could be achieved at room temperature. More importantly, the less reactive, but more broadly available, aryl chlorides became accessible substrates. Tri-tert-butylphosphine has become a privileged ligand that has found application in a wide range of late transition-metal catalyzed coupling reactions. This success has led to the use of numerous monodentate trialkylphosphines in cross-coupling reactions. This review will discuss the general properties and features of monodentate trialkylphosphines and their application in cross-coupling reactions of C–X and C–H bonds.

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Synthesis of Coumarin Derivatives as Versatile Scaffolds for GSK-3β Enzyme Inhibition

Current Topics in Medicinal Chemistry ◽

10.2174/1568026619666191019105349 ◽

2020 ◽

Vol 20 (2) ◽

pp. 153-160 ◽

Cited By ~ 1

Author(s):

Carla S. Francisco ◽

Clara L. Javarini ◽

Iatahanderson de S. Barcelos ◽

Pedro A.B. Morais ◽

Heberth de Paula ◽

...

Keyword(s):

Kinase Inhibitors ◽

Glycogen Synthase ◽

Synthetic Methods ◽

Kinase Assay ◽

Crystallographic Structure ◽

Coumarin Derivatives ◽

Enzymatic Production ◽

Docking Simulations ◽

In Silico Studies ◽

Gsk 3Β

Background: Glycogen synthase kinase-3 (GSK-3) is involved in the phosphorylation and inactivation of glycogen synthase. GSK-3 inhibitors have been associated with a variety of diseases, including Alzheimer´s disease (AD), diabetes type II, neurologic disorders, and cancer. The inhibition of GSK-3β isoforms is likely to represent an effective strategy against AD. Objective: The present work aimed to design and synthesize coumarin derivatives to explore their potential as GSK-3β kinase inhibitors. Method: The through different synthetic methods were used to prepare coumarin derivatives. The GSK-3β activity was measured through the ADP-Glo™ Kinase Assay, which quantifies the kinasedependent enzymatic production of ADP from ATP, using a coupled-luminescence-based reaction. A docking study was performed by using the crystallographic structure of the staurosporine/GSK-3β complex [Protein Data Bank (PDB) code: 1Q3D]. Results: The eleven coumarin derivatives were obtained and evaluated as potential GSK-3β inhibitors. Additionally, in silico studies were performed. The results revealed that the compounds 5c, 5d, and 6b inhibited GSK-3β enzymatic activity by 38.97–49.62% at 1 mM. The other coumarin derivatives were tested at 1 mM, 1 µM, and 1 nM concentrations and were shown to be inhibitor candidates, with significant IC50 (1.224–6.875 µM) values, except for compound 7c (IC50 = 10.809 µM). Docking simulations showed polar interactions between compound 5b and Lys85 and Ser203, clarifying the mechanism of the most potent activity. Conclusion: The coumarin derivatives 3a and 5b, developed in this study, showed remarkable activity as GSK-3β inhibitors.

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Chemistry of Unsymmetrical C1-Substituted Oxabenzonorbornadienes

Current Organic Synthesis ◽

10.2174/1570179417666210105121115 ◽

2021 ◽

Vol 17 ◽

Author(s):

Austin Pounder ◽

Angel Ho ◽

Matthew Macleod ◽

William Tam

Keyword(s):

Transition Metal ◽

Metal Complexes ◽

Transition Metal Complexes ◽

Substituent Effects ◽

Face Selectivity ◽

Transition Metal Catalyzed ◽

Catalyzed Reactions ◽

Metal Catalyzed ◽

Synthetic Intermediate

: Oxabenzonorbornadiene (OBD) is a useful synthetic intermediate which can be readily activated by transition metal complexes with great face selectivity due to its dual-faced nature and intrinsic angle strain on the alkene. To date, the understanding of transition-metal catalyzed reactions of OBD itself has burgeoned; however, this has not been the case for unsymmetrical OBDs. Throughout the development of these reactions, the nature of C1-substituent has proven to have a profound effect on both the reactivity and selectivity of the outcome of the reaction. Upon substitution, different modes of reactivity arise, contributing to the possibility of multiple stereo-, regio-, and in extreme cases, constitutional isomers which can provide unique means of constructing a variety of synthetically useful cyclic frameworks. To maximize selectivity, an understanding of bridgehead substituent effects is crucial. To that end, this review outlines hitherto reported examples of bridgehead substituent effects on the chemistry of unsymmetrical C1-substituted OBDs.

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Transition metal-catalyzed reactions of N-sulfinyl imines

Tetrahedron Letters ◽

10.1016/j.tetlet.2021.153104 ◽

2021 ◽

pp. 153104

Author(s):

Francisco Foubelo ◽

Carmen Nájera ◽

José M. Sansano ◽

Miguel Yus

Keyword(s):

Transition Metal ◽

Transition Metal Catalyzed ◽

Catalyzed Reactions ◽

Metal Catalyzed

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Chiral Aziridine Sulfide N(sp3),S-Ligands for Metal-Catalyzed Asymmetric Reactions

Symmetry ◽

10.3390/sym13030502 ◽

2021 ◽

Vol 13 (3) ◽

pp. 502

Author(s):

Agata J. Pacuła-Miszewska ◽

Anna Laskowska ◽

Anna Kmieciak ◽

Mariola Zielińska-Błajet ◽

Marek P. Krzemiński ◽

...

Keyword(s):

Metal Binding ◽

Electronic Effect ◽

Asymmetric Reactions ◽

Addition Reactions ◽

Phenyl Sulfide ◽

Enantiomeric Ratio ◽

Catalyzed Reactions ◽

Metal Catalyzed ◽

Sulfide Group

A series of new bidentate N,S-ligands—aziridines containing a para-substituted phenyl sulfide group—was synthesized and evaluated in the Pd-catalyzed Tsuji–Trost reaction and addition of diethylzinc and phenylethynylzinc to benzaldehyde. A high enantiomeric ratio for the addition reactions (up to 94.2:5.8) was obtained using the aziridine ligand bearing a p-nitro phenyl sulfide group. Collected results reveal a specific electronic effect that, by the presence of particular electron-donating or electron-withdrawing groups in the PhS- moiety, influences the σ-donor–metal binding and the enantioselectivity of the catalyzed reactions.

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