7515-24-4

Upstream product

• 1711-05-3 m-anisoyl chloride 
• 21204-67-1 methyl (triphenylphosphoranylidene)acetate 
• 67-56-1 methanol 
• 7621-89-8 3-(3-methoxyphenyl)propiolic acid 
• 18107-18-1 diazomethyl-trimethyl-silane 
• 766-85-8 3-methoxy-1-iodobenzene 
• 922-67-8 propynoic acid methyl ester 
• 591-31-1 3-methoxy-benzaldehyde 
• 74-88-4 methyl iodide 
• 768-70-7 1-ethynyl-3-methoxybenzene 
• 90965-06-3 dimethyl 1-(1-diazo-2-oxopropyl)phosphonate 
• 79-22-1 methyl chloroformate 
• 2398-37-0 3-methoxyphenyl bromide 
• 98332-36-6 methyl 3-(3-methoxyphenyl)-3-oxo-2-(triphenylphosphoranylidene)propanoate 

Downstream Products

• 7621-89-8 3-(3-methoxyphenyl)propiolic acid 
• 732211-88-0 (1S,2S)-2-(3-Methoxy-phenyl)-cyclopropylamine 

Relevant academic research and scientific papers

Organocatalytic trans Phosphinoboration of Internal Alkynes

We report the first trans phosphinoboration of internal alkynes. With an organophosphine catalyst, alkynoate esters and the phosphinoboronate Ph2P-Bpin are efficiently converted into the corresponding trans-α-phosphino-β-boryl acrylate products in moderate to good yield with high regio- and Z-selectivity. This reaction operates under mild conditions and demonstrates good atom economy, requiring only a modest excess of the phosphinoboronate. X-ray crystallography experiments allowed structural assignment of the unprecedented and densely functionalized (Z)-α-phosphino-β-boryl acrylate products.

Oxidant- and additive-free simple synthesis of 1,1,2-triiodostyrenes by one-pot decaroboxylative iodination of propiolic acids

A metal- and oxidant-free facile synthesis of a range of 1,1,2-triiodostryrene derivatives has been developed which utilizes a simple decarboxylative triiodination of propiolic acids using molecular iodine and sodium acetate in a one-pot manner. Electron-

Efficient Access to Chiral β-Borylated Carboxylic Esters via Rh-Catalyzed Hydrogenation

Rh/bisphosphine?thiourea ligand (ZhaoPhos)-catalyzed asymmetric hydrogenation of (Z)-β-substituted-β-boryl-α,β-unsaturated esters was successfully developed, furnishing a variety of chiral β-borylated carboxylic esters with high yields and excellent enantioselectivities (up to 99% yield and >99% ee). The gram-scale asymmetric hydrogenation was performed efficiently in the presence of only 0.05 mol% (S/C=2 000) catalyst loading with full conversion, 99% yield and 99% ee. Moreover, the hydrogenation product was easily converted to other versatile synthetic intermediates, such as methyl (S)-3-hydroxy-3-phenylpropanoate and methyl (S)-3-(furan-2-yl)-3-phenylpropanoate. (Figure presented.).

Salt-Free Strategy for the Insertion of CO2 into C?H Bonds: Catalytic Hydroxymethylation of Alkynes

A copper(I) catalyst enables the insertion of carbon dioxide into alkyne C?H bonds by using a suitable organic base with which hydrogenation of the resulting carboxylate salt with regeneration of the base becomes thermodynamically feasible. In the presence of catalytic copper(I) chloride/4,7-diphenyl-1,10-phenanthroline, polymer-bound triphenylphosphine, and 2,2,6,6-tetramethylpiperidine as the base, terminal alkynes undergo carboxylation at 15 bar CO2 and room temperature. After filtration, the ammonium alkynecarboxylate can be hydrogenated to the primary alcohol and water at a rhodium/molybdenum catalyst, regenerating the amine base. This demonstrates the feasibility of a salt-free overall process, in which carbon dioxide serves as a C1 building block in a C?H functionalization.

Palladium-Catalyzed Ylidyl-Carbonylation of Aryl Halides to Produce α-Acylphosphoranes

An efficient synthesis of α-acylphosphoranes by palladium-catalyzed carbonylation of aryl iodides with carbon monoxide and stabilized phosphonium ylides has been developed. Featuring 44 examples, the protocol displayed a wide substrate scope under mild reaction conditions, showcasing its potential in synthetic organic chemistry.

Application and scope of Schreiber's gold(I)-catalyzed α-pyrone synthesis to ring a aromatic podolactones

Schreiber's gold(I)-catalyzed synthesis of α-pyrones was adapted to the total synthesis of a ring A aromatic podolactone, urbalactone. The scope of the acetylenic ester partner in the formation of α-pyrones was studied. The total synthesis features, as ke

Pyranone, thiopyranone, and pyridone inhibitors of phosphatidylinositol 3-kinase related kinases. Structure-activity relationships for DNA-dependent protein kinase inhibition, and identification of the first potent and selective inhibitor of the ataxia telangiectasia mutated kinase

Structure-activity relationships have been investigated for inhibition of DNA-dependent protein kinase (DNA-PK) and ATM kinase by a series of pyran-2-ones, pyran-4-ones, thiopyran-4-ones, and pyridin-4-ones. A wide range of IC50 values were observed for pyranones and thiopyranones substituted at the 6-position, with the 3- and 5-positions proving intolerant to substitution. Related pyran-2-ones, pyran-4-ones, and thiopyran-4-ones showed similar IC50 values against DNA-PK, whereas the pyridin-4-one system proved, in general, ineffective at inhibiting DNA-PK. Extended libraries exploring the 6-position of 2-morpholinopyran-4-ones and 2-morpholino- thiopyrano-4-ones identified the first highly potent and selective ATM inhibitor 2-morpholin-4-yl-6-thianthren-1-yl-pyran-4-one (151C; ATM; IC50 = 13 nM) and revealed constrained SARs for ATM inhibition compared with DNA-PK. One of the most potent DNA-PK inhibitors identified, 2-(4-methoxyphenyl)-6- (morpholin-4-yl)pyran-4-one (16; DNA-PK; IC50 = 220 nM) effectively sensitized HeLa cells to the topoisomerase II inhibitor etoposide in vitro.

Transition-metal-catalyzed carbon-nitrogen and carbon-carbon bond-forming reactions

One aspect of the present invention relates to ligands for transition metals. A second aspect of the present invention relates to the use of catalysts comprising these ligands in various transition-metal-catalyzed carbon-heteroatom and carbon-carbon bond-forming reactions. The subject methods provide improvements in many features of the transition-metal-catalyzed reactions, including the range of suitable substrates, number of catalyst turnovers, reaction conditions, and efficiency. For example, improvements have been realized in transition metal-catalyzed: aryl amination reactions; aryl amidation reactions; Suzuki couplings; and Sonogashira couplings. In certain embodiments, the invention relates to catalysts and methods of using them that operate in aqueous solvent systems.

General catalysts for the Suzuki-Miyaura and Sonogashira coupling reactions of aryl chlorides and for the coupling of challenging substrate combinations in water

Amphiphilic phosphine ligands (see structures; Cy = cyclohexyl) were prepared and utilized in palladium-catalyzed Suzuki-Miyaura and Sonogashira coupling reactions in water or water/organic biphasic solvents, providing excellent yields of functionalized b

Preparation of 1-aryl-2-bromo-3,3-difluorocyclopropenes

1-Aryl-2-bromo-3,3-difluorocyclopropanes were prepared from the reaction of 2′,2′-difluorostyrene and dibromocarbene instead of from 1-aryl-2-haloacetylenes and difluorocarbene. These results are rationalised by the energy gap between HOMO(styrene), HOMO(acetylene) and LUMO(CX2). The title compounds were converted to methyl arylpropynoate in MeOH solution in quantitative yield.