7515-18-6

Upstream product

• 67-56-1 methanol 
• 3240-10-6 (4-chlorophenyl)propiolic acid 
• 59719-19-6 5-(4-chlorophenyl)-2,4-dihydro-3H-pyrazol-3-one 
• 22511-02-0 5-(4-chlorophenyl)-1,2-dihydro-3H-pyrazol-3-one 
• 873-73-4 4-n-chlorophenylacetylene 
• 201230-82-2 carbon monoxide 
• 7647-01-0 hydrogenchloride 
• 96277-02-0 methyl 3-(4-chlorophenyl)-3-oxo-2-(triphenylphosphoranylidene)propanoate 
• 122-01-0 4-chloro-benzoyl chloride 
• 637-87-6 1-Chloro-4-iodobenzene 
• 79-22-1 methyl chloroformate 
• 22027-53-8 methyl 3-(4-chlorophenyl)-3-oxopropanoate 
• 922-67-8 propynoic acid methyl ester 
• 124-38-9 carbon dioxide 

Downstream Products

• 115665-06-0 5-(4-Chloro-phenyl)-3-phenyl-isoxazole-4-carboxylic acid methyl ester 
• 79230-03-8 (Z)-3-(4-Chloro-phenyl)-3-p-tolylamino-acrylic acid methyl ester 
• 77663-56-0 3-(4-Chloro-phenyl)-propynoic acid {2-[3-(4-chloro-phenyl)-propynoylamino]-ethyl}-amide 
• 79230-04-9 methyl (Z)-β-(o-aminoanilino)-p-chlorocinnamate 
• 115665-08-2 5-(4-Chloro-phenyl)-3-(4-methoxy-phenyl)-isoxazole-4-carboxylic acid methyl ester 
• 1032041-66-9 methyl 1,4,5,6-tetramethyl-3-(4'-chlorophenyl)-bicyclo[2.2.0]hexa-2,5-diene-2-carboxylate 
• 1174523-57-9 (R)-methyl 8a-(but-3-enyl)-5-(4-chlorophenyl)-7-oxo-1,2,3,7,8,8a-hexahydroindolizine-6-carboxylate 
• 1174523-55-7 (R)-methyl 5-(4-chlorophenyl)-7-oxo-1,2,3,7,8,8a-hexahydroindolizine-6-carboxylate 

Relevant academic research and scientific papers

De Novo Construction of Substituted Terephthalates via Phosphine Catalyzed Domino Benzannulation Reactions

The robustness of phosphine catalysis enabling the domino benzannulation reactions of allenoates with enamines is described. A broad array of substituted terephthalates were delivered under simple and practical reaction conditions. Furthermore, the reaction could be carried out on a gram scale with higher yield, and various conversions of the terephthalate products demonstrate the versatility of this transformation. (Figure presented.).

Au(I) Catalyzed Synthesis of Densely Substituted Pyrazolines and Dihydropyridines via Sequential Aza-Enyne Metathesis/6π-Electrocyclization

A gold(I) autotandem catalysis protocol is reported for the de novo synthesis of densely substituted pyrazolines and dihydropyridines from the corresponding imine derivatives in a highly regioselective fashion via a one-pot aza-enyne metathesis/6π-electrocyclization sequence. The substituents on the nitrogen atom of the imine perfectly control the reaction pathways from the pivotal 1-azabutadiene intermediate; thus, carbazates were converted into pyrazolines via 6π-electrocyclization of α,β-unsaturated hydrazones, while aryl imines provided dihydropyridines via 6π-electrocyclization of 3-azahexatrienes.

Z-Selective phosphine promoted 1,4-reduction of ynoates and propynoic amides in the presence of water

Phosphine-mediated reductions of substituted propynoic esters and amides in the presence of water yield the partially reduced α,β-unsaturated esters and amides with highZ-selectivity. The competitivein situ ZtoE-isomerization of the product in some cases lowers theZtoEratios of the isolated α,β-unsaturated carbonyl products. Reaction time and the amounts of phosphine and water in the reaction mixture are the key experimental factors which control the selectivity by preventing or reducing the rates ofZ- toE-product isomerization. Close reaction monitoring enables isolation of theZ-alkenes with high selectivities. The computational results suggest that the reactions could be highlyZ-selective owing to the stereoselective formation of theE-P-hydroxyphosphorane intermediate.

Enantioselective Fluorination of α-Branched β-Ynone Esters Using a Cinchona-Based Phase-Transfer Catalyst

Herein, we report the fluorination of α-branched β-ynone esters to afford their corresponding quaternary fluorinated products with good enantioselectivity (ee = 73-90%) using a cinchona-based phase-transfer catalyst. α-Branched β-ynone esters possess a highly acidic α-proton and form their corresponding enolate as a single isomer, which allows the enantioselective fluorination reaction to occur under standard cinchona-based phase-transfer catalyst conditions. Moreover, the obtained α-fluorinated product can be treated with [(SPhos)AuNTf2] (1 mol %) to afford a fluorinated 3,5-diketo carboxylic acid.

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.).

Synthesis of Chiral β-Borylated Carboxylic Esters via Nickel-Catalyzed Asymmetric Hydrogenation

The highly efficient Ni-catalyzed asymmetric hydrogenation of β-boronic ester substituted-α,β-unsaturated carboxylic esters was successfully developed using (S,S)-Ph-BPE as the ligand. A series of chiral β-borylated carboxylic esters were obtained with high yields (94%-99% yields) and excellent enantioselectivities (89%-99% ee). The gram-scale asymmetric hydrogenation with a low catalyst loading (0.25 mol %) and synthetic transformation of hydrogenation product demonstrated the great synthetic utility of this methodology.

Alkynylboration Reaction Leading to Boron-Containing π-Extended cis-Stilbenes as a Highly Tunable Fluorophore

An unprecedented boron-containing fluorophore, π-extended cis-stilbene, obtained via alkynylboration reaction of alkynamide is reported. Boron-containing π-extended cis-stilbenes emit fluorescence with high quantum yields in the solid state and exhibit aggregation-induced emission enhancement. The broad substrate scope of the alkynylboration reaction offers facile access to electronically diverse structures, enabling fine-tuning of light absorption/emission characteristics. The boron-containing π-extended cis-stilbene with a diphenylamino group displays solvatofluorochromism via an intramolecular charge-transfer transition.

Cobalt(III)-Catalyzed Intermolecular Carboamination of Propiolates and Bicyclic Alkenes via Non-Annulative Redox-Neutral Coupling

A cobalt(III)-catalyzed, redox-neutral, intermolecular carboamination of propiolates and bicyclic alkenes was developed. This non-annulative coupling strategy features atom economy, high regioselectivity, good yields, and functional groups tolerance. Such a carboamination reaction was applied to modified phenols from the corresponding phenols under mild conditions.