109475-18-5

Upstream product

• 150-19-6 O-methylresorcine 
• 140-10-3 (E)-3-phenylacrylic acid 
• 531-59-9 7-methoxycoumarin 
• 98-80-6 phenylboronic acid 

Downstream Products

• 1393362-05-4 4-phenyl-7-methoxy-4H-chromene 
• 2555-31-9 7-methoxy-4-phenyl-2H-chromen-2-one 

Relevant academic research and scientific papers

Rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids to coumarins: Asymmetric synthesis of (R)-tolterodine

(Chemical Equation Presented) Rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids to coumarins proceeded with high enantioselectivity in the presence of a rhodium catalyst (3 mol %) generated from Rh(acac)(C 2H4)2 and (R)-Segphos to give the corresponding (R)-4-arylchroman-2-ones in over 99% ee. This asymmetric reaction was applied to the synthesis of (R)-tolterodine.

Highly Efficient and Single Step Synthesis of 4-Phenylcoumarins and 3,4-Dihydro-4-phenylcoumarins over Montmorillonite K-10 Clay, under Microwave Irradiation

A simple, elegant and one-pot synthesis of 3,4-dihydro-4-phenylcoumarins, 4-phenylcoumarins and their derivatives by making use of solid support, montmorillonite K-10 clay in conjunction with microwave irradiation is described.

Computationally-Led Ligand Modification using Interplay between Theory and Experiments: Highly Active Chiral Rhodium Catalyst Controlled by Electronic Effects and CH–π Interactions

A chiral ligand for the rhodium-catalyzed asymmetric 1,4-addition of an arylboronic acid to a coumarin substrate that could markedly reduce catalyst loading was developed using interplay between theoretical and experimental approaches. Evaluation of the transition states for insertion and for hydrolysis of intermediate complexes (which were emphasized in response to the experimental results) using DFT calculations at the B97D/6-31G(d) level with the LANL2DZ basis set for rhodium revealed that: (i) the electron-poor nature of the ligands and (ii) CH–π interactions between the ligand and coumarin substrates played significant roles in both acceleration of insertion and inhibition of ArB(OH)2 decomposition (protodeboronation). The computationally-designed ligand, incorporating the above information, enabled a decrease in the catalyst loading to 0.025 mol% (S/C=4,000), which is less than one one-hundredth relative to past catalyst loadings of typically 3 mol%, with almost complete enantioselectivity. Furthermore, the gram-scale synthesis of the urological drug, (R)-tolterodine (l)-tartrate, was demonstrated without the need of intermediate purification. (Figure presented.).

Organic Solvent-free Asymmetric 1,4-Addition in Liquid- or Solid-State using Conventional Stirring Catalyzed by a Chiral Rhodium Complex Developed as a Homogeneous Catalyst

Organic solvent-free asymmetric 1,4-addition of arylboronic acids to enone substrates was performed by using a chiral rhodium complex catalyst developed as a homogeneous catalyst. Reactions catalyzed by [RhOH(cod)]2 with chiral diphosphine ligands in liquid- or solid-state proceeded to give chiral 1,4-adducts in high yield with enantioselectivities up to ca. 100 % ee by conventional stirring without mechanochemistry such as ball milling. The solid-state reactions under a static condition also proceeded, but with a slight decrease in enantioselectivity of the 1,4-adduct. SEM observations of the solid-state reactions indicated that no nanoparticles catalyst was generated. The organic solvent-free reaction could be applied to gram-scale synthesis by performing a greener purification using a minimum necessary organic solvent.

Palladium Catalyzed Enantioselective Hayashi-Miyaura Reaction for Pharmaceutically Important 4-Aryl-3,4-dihydrocoumarins

The first palladium-catalyzed asymmetric addition of arylboronic acids to coumarins was successfully established, providing a straightforward asymmetric approach to achieving pharmaceutically important 4-aryl-3,4-dihydrocoumarins. This methodology features easily accessible and bench-stable ligands, a wide substrate scope, mild conditions, and accommodation of electron-withdrawing arylboronic acids.

Short synthesis of cytotoxic 4-arylcoumarins

A short synthesis of cytotoxic 4-arylcoumarins via condensation of phenols with cinnamic acids in the presence of CF3COOH, followed by dehydrogenation with DDQ, is described. Copyright Taylor & Francis Group, LLC.