955-10-2

Usage

Synthesis Reference(s)

Journal of Heterocyclic Chemistry, 16, p. 97, 1979 DOI: 10.1002/jhet.5570160120Synthetic Communications, 17, p. 341, 1987 DOI: 10.1080/00397918708077315Tetrahedron, 44, p. 6387, 1988 DOI: 10.1016/S0040-4020(01)89826-4

InChI:InChI=1/C15H10O2/c16-15-13(11-6-2-1-3-7-11)10-12-8-4-5-9-14(12)17-15/h1-10H

Upstream product

• 5663-67-2 2-acetoxybenzaldehyde 
• 114-70-5 sodium phenylacetate 
• 100-34-5 benzene diazonium chloride 
• 91-64-5 coumarin 
• 67-64-1 acetone 
• 94-36-0 dibenzoyl peroxide 
• 108-24-7 acetic anhydride 
• 90-02-8 salicylaldehyde 
• 140-29-4 phenylacetonitrile 
• 103-82-2 phenylacetic acid 
• 3442-15-7 1,4-diphenylbutane-1,3-dione 
• 67-56-1 methanol 
• 67231-69-0 3-phenyl-2H-chromen-2-imine 
• 64-17-5 ethanol 

Downstream Products

• 97433-31-3 3-(2-hydroxy-phenyl)-2-phenyl-acrylonitrile 
• 186552-85-2 3-phenyl-2H-1-benzopyran-2-ol 
• 20890-72-6 Z-3-(o-methoxyphenyl)-2-phenyl propenoic acid 
• 261633-61-8 methyl Z-3-(o-methoxyphenyl)-2-phenyl propenoate 
• 20890-72-6 (E)-2-phenyl-3-(2-methoxyphenyl)propenoic acid 
• 13130-21-7 3-(2-hydroxyphenyl)-2H-chromen-2-one 
• 1620681-03-9 3-(2-bromophenyl)-2H-chromen-2-one 

Relevant academic research and scientific papers

Dual Role of Oxoaldehydes: Divergent Synthesis of 3-Aryl- and 3-Aroylcoumarins

A facile and efficient synthetic approach to various valuable 3-aryl- and 3-aroylcoumarins by the direct arylation and aroylation of coumarins with glyoxals in a metal-free manner is presented. The aryl glyoxal is for the first time recognized to serve as an aryl surrogate in addition to its role as an aroyl transfer reagent via a simple switch in reaction conditions. The approach accommodates a broad substrate scope and high yields of the two types of cross-coupling reactions starting from identical starting materials.

Bulky Selenium Ligand Stabilized Trans-Palladium Dichloride Complexes as Catalyst for Silver-Free Decarboxylative Coupling of Coumarin-3-Carboxylic Acids

This report describes the syntheses of three new trans-palladium dichloride complexes of bulky selenium ligands. These complexes possess a Cl?Pd?Cl rotor spoke attached to a Se?Pd?Se axle. The new ligands and palladium complexes (C1?C3) were characterized with the help of NMR, HRMS, UV-Vis., IR, and elemental analysis. The single-crystal structure of metal complex C2 confirmed a square planar geometry of complex with trans-orientation. The X-ray structure revealed intramolecular secondary interactions (SeCH—Cl) between chlorine of PdCl2 and CH2 proton of selenium ligand. Variable-temperature NMR data shows coalescence of diastereotopic protons, which indicates pyramidal inversion of selenium atom at elevated temperature. The relaxed potential energy scan of C2 suggests a rotational barrier of ～12.5 kcal/mol for rotation of chlorine atom through Cl?Pd?Cl rotor. The complex C3 possesses dual intramolecular secondary interactions (OCH2—Cl and SeCH2—Cl) with stator ligand. Molecular rotor C2 was found to be a most efficient catalyst for the decarboxylative Heck-coupling under mild reaction conditions. The protocol is applicable to a broad range of substrates with large functional group tolerance and low catalyst loading (2.5 mol %). The mechanism of decarboxylative Heck-coupling reaction was investigated through experimental and computational studies. Importantly the reaction works under silver-free conditions which reduces the cost of overall protocol. Further, the catalyst also worked for decarboxylative arylation and decarboxylative Suzuki-Miyaura coupling reactions with good yields of the coupled products.

Looking for new xanthine oxidase inhibitors: 3-Phenylcoumarins versus 2-phenylbenzofurans

Overproduction of uric acid in the body leads to hyperuricemia, which is also closely related to gout. Uric acid production can be lowered by xanthine oxidase (XO) inhibitors. Inhibition of XO has also been proposed as a mechanism for improving cardiovascular health. Therefore, the search for new efficient XO inhibitors is an interesting topic in drug discovery. 3-Phenylcoumarins and 2-phenylbenzofurans are privileged scaffolds in medicinal chemistry. Their structural similarity makes them interesting molecules for a comparative study. Methoxy and nitro substituents were introduced in both scaffolds. The current study gives some insights into the synthesis and biological activity of these molecules against this important target. For the best compound of the series, the 3-(4-methoxyphenyl)-6-nitrocoumarin (4), the IC50 value, type of inhibition, cytotoxicity on B16F10 cells and ADME theoretical properties, were determined. Docking studies were also performed in order to better understand the interactions of this molecule with the XO binding pocket. This work is a preliminary screening for further design and synthesis of new non-purinergic derivatives as potential compounds involved in the inflammatory suppression, specially related to gout.

Chlorophyll-catalyzed photochemical regioselective coumarin C-H arylation with diazonium salts

This communication describes the development of a mild method for the cross-coupling of the C3-position of coumarin with an array of diazonium salts mediated by chlorophyll as a biocatalyst via visible light catalysis. A natural pigment such as chlorophyll is used as a green photosensitizer and environmentally benign catalyst. This general and easy procedure provides a transition-metal-free alternative for the formation of 3-aryl coumarin derivatives at room temperature with good to excellent yields. This journal is

Visible-light-driven copper-catalyzed aerobic oxidative cascade cyclization of N-tosylhydrazones and terminal alkynes: Regioselective synthesis of 3-arylcoumarins

We present the first example of sustainable, intuitive, highly regioselective, visible-light-driven copper catalyzed aerobic oxidative cascade cyclization of N-tosylhydrazones with terminal alkynes for the preparation of 3-arylcoumarins at room temperature. This operationally simple methodology has been successfully applied to a wide range of N-tosylhydrazones and alkynes (49 examples), and proceeds well to afford biologically active compounds, such as monoamine oxidase B (MAO-B) inhibitor and horseradish peroxidase (HRP) inhibitor, in satisfactory yields under mild conditions. Furthermore, mechanistic studies suggest that the reaction proceeds via a copper(ii)-superoxo or -peroxo complex mediated oxidative annulation of terminal alkynes, as evidenced by 18O2 isotopic-labelling experiments.

Direct C-3 alkylation of coumarins via decarboxylative coupling with carboxylic acids

A new method for selective C-3 alkylation of coumarins using carboxylic acids as alkyl sources is reported. This process offers a practical method for the facile construction of 3-alkyl coumarins with a broad substrate scope. The reaction works under metal-free and aqueous media and both cyclic and acyclic aliphatic carboxylic acids participate in this radical C-C cross coupling reaction.

Zn(II)-Catalyzed One-Pot Synthesis of Coumarins from Ynamides and Salicylaldehydes

A highly efficient and straightforward synthesis of diversely substituted coumarins from ynamides and salicylaldehydes in the presence of Zn(II) catalyst has been developed. The sulfonamide moiety of ynamides was successfully recycled in this process, serving as an effective traceless directing group for high regioselectivity in the bond-forming event. The advantages of this protocol are good functional group tolerance, broad substrate scope, simple and high-yielding reaction, recovery/reuse of the sulfonamides, low catalyst loading of inexpensive catalyst, and, by these merits, a more cost-effective and greener process.

Three-component one-pot synthesis of N-arylsulfonyl-2-iminocoumarins

A one-pot, synthesis of N-arylsulfonyl-2-iminocoumarins is developed at ambient temperature by the reaction of 2-hydroxybenzaldehydes, arylacetonitriles, and aryl sulfonyl chlorides using DABCO as a base in a bio-mass-derived green solvent 2-MethylTHF. A simple telescoped process in which 2H-chromen-2-imines are formed in situ by the condensation of 2-hydroxybenzaldehyde and arylacetonitriles. The formed imines are further reacted with arylsulfonyl chlorides in a one-pot approach to obtain the target compounds. This protocol provides access to 3-aryl-N-arylsulfonyl-2-iminocoumarins in a practical and environmentally benign way avoiding cumbersome steps of intermediate syntheses and purifications.

Pd-catalysed carbonylative annulation of salicylaldehydes with benzyl chlorides using N-formylsaccharin as a CO surrogate

A convenient and highly efficient Pd-catalysed carbonylative annulation of salicylaldehydes with benzyl chlorides to afford the corresponding 3-arylcoumarins in good to excellent yields has been developed. Importantly, the protocol utilizes a commercially available, low cost, solid and easy to handle N-formylsaccharin as an alternative to the highly toxic CO gas.

Method for synthesizing coumarin compound in one step

The invention discloses a method for synthesizing a coumarin compound in one step. Starting from simple and easy-to-obtain starting materials, the method disclosed by the invention cost-efficiently and efficiently synthesizes the 3,4-substrituted coumarin compound under mild conditions. With phenol as a material, a phenoxyamide compound is obtained, the phenoxyamide compound, carbon monoxide and alkyne are heated to 45 DEG C to 70 DEG C under normal pressure, so that reaction takes place, and thereby the 3,4-substrituted coumarin compound is obtained in one step. In reaction, an external oxidant does not need to be added, conditions are mild, the reaction yield is high, and the adaptability is good. In case of reaction with asymmetric alkyne, the 3-site and the 4-site of the obtained coumarin compound have unique selectivity.