1154057-90-5

Upstream product

• 124-38-9 carbon dioxide 
• 536-74-3 phenylacetylene 
• 2687-12-9 cinnamyl chloride 
• 50685-89-7 1-bromomethyl-4-styrylbenzene 
• 104-54-1 3-Phenylpropenol 
• 637-44-5 phenylpropyolic acid 

Downstream Products

• 10568-29-3 9-Phenylnaphtho<2,3-c>furan-1(3H)-one 
• 10568-28-2 9-Phenyl-3a,4-dihydronaphtho<2,3-c>furan-1(3H)-one 

Relevant academic research and scientific papers

Development of magnesium oxide-silver hybrid nanocatalysts for synergistic carbon dioxide activation to afford esters and heterocycles at ambient pressure

Multi-metallic hybrid nanocatalysts consisting of a porous metal oxide host and metal satellite guests serve as a scaffold for multi-step transformations of divergent and energy-challenging substrates. Here we have developed a 3D porous MgO framework (Lewis basic host) with Ag0 nanoparticles (noble metal guest) for ambient pressure activation and insertion of CO2 into unsaturated alkyne substrates. The hybrid MgO@Ag-x (x = 2, 5, 7, 8 at% Ag) catalysts are synthesized by impregnating Ag+ ions in porous MgO cubes followed by reduction using NaBH4. Morphological (SEM, TEM, EDX mapping) and structural (PXRD, XPS) characterization reveal that the micron-sized hybrid cubes derive from self-assembly of ～100 nm (edge length) MgO cubes decorated with ～5 to 25 nm Ag0 NPs. Detailed XPS analysis illustrates Ag0 is present in two forms, 2 into aryl alkynes followed by SN2 coupling with allylic chlorides to afford a wide range of ester and lactone heterocycles in excellent yields (61-93%) and with low E-factor (2.8). The proposed mechanism suggests a CO2 capture and substrate assembly role for 3D porous MgO while Ag0 performs the key activation of alkyne and CO2 insertion steps. The catalyst is recyclable (5×) with no significant loss of product yield. Overall, these results demonstrate viable approaches to hybrid catalyst development for challenging conversions such as CO2 utilization in a green and sustainable manner.

Ynamide-Mediated Intermolecular Esterification

An ynamide-mediated one-pot, two-step intermolecular esterification via the condensation of carboxylic acids with nucleophilic hydroxyl species was reported. A broad substrate scope with respect to carboxylic acids, alcohols, and phenols was observed. The α-acyloxyenamide intermediates formed by the addition of carboxylic acids to ynamides proved to be effective acylating reagents for the esterification of alcohol and phenol derivatives with the assistance of base catalysis. Notably, the racemization of the α-chiral center of carboxylic acids can be avoided.

Unprecedented Multicomponent Organocatalytic Synthesis of Propargylic Esters via CO2 Activation

An efficient and straightforward organocatalytic method for the direct, multicomponent carboxylation of terminal alkynes with CO2 and organochlorides, towards propargylic esters, is reported for the first time. 1,3-Di-tert-butyl-1H-imidazol-3-ium chloride, a simple, widely-available, stable, and cost-efficient N-heterocyclic carbene (NHC) precursor salt was used as the (pre)catalyst. A wide range of phenylacetylenes, bearing electron-withdrawing or electron-donating substituents, react with allyl-chlorides, benzyl chlorides, or 2-chloroacetates, providing the corresponding propargylic esters in low to excellent yields. DFT calculations on the mechanism of this transformation indicate that the reaction is initiated with the formation of an NHC-carboxylate, by addition of the carbene to a molecule of CO2. Then, the nucleophilic addition of this species to the corresponding chlorides has been computed to be the rate limiting step of the process.

Ordered Mesoporous CeO2-supported Ag as an Effective Catalyst for Carboxylative Coupling Reaction Using CO2

Ag/Mesoporous CeO2 (Ag/M?CeO2) catalysts were synthesized through the gas bubbling-assisted membrane reduction (GBMR) method and characterized by XRD, ICP-OES, N2 adsorption-desorption, XPS, Raman spectroscopy, TEM, HRTEM, HAADF-STEM and CO2-TPD. Ag/M?CeO2 catalysts contain uniform mesoporous structure, large surface area and oxygen vacancies, which promote the dispersion of Ag nanoparticles. Density functional theory (DFT) calculations indicate that Ag nanoparticles supported on M?CeO2 could facilitate the formation of oxygen vacancies, which result in higher CO2 adsorption capacity. With the most oxygen vacancies and the well-dispersed Ag active species, Ag (3.12 %)/M?CeO2 exhibits high efficiency for the carboxylative coupling of terminal alkynes, chloride compounds and CO2 under mild reaction conditions (60 °C, 0.5 MPa), affording a wide range of functionalized 2-alkynoates in good yields.

Silver-catalyzed one-pot synthesis of benzyl 2-alkynoates under ambient pressure of CO2and ligand-free conditions

The carboxylative coupling of aryl/alkyl terminal alkynes, CO2and benzyl halides was investigated using silver iodide as the catalyst and Cs2CO3as the base in CH3CN under ligand-free conditions. This reaction protocol shows a wide substrate scope and high functional group tolerance ability for benzyl halides, in which various functionalized benzyl 2-alkynoates were achieved in good yields. This one-pot, ligand-free and CH3CN mediated reaction proved to be easy to handle and could be facilitated under atmospheric CO2pressure.

Intramolecular dehydro-diels-alder reaction affords selective entry to arylnaphthalene or aryldihydronaphthalene lignans

Intramolecular dehydro-Diels-Alder (DDA) reactions are performed affording arylnaphthalene or aryldihydronaphthalene lactones selectively as determined by choice of reaction solvent. This constitutes the first report of an entirely selective formation of arylnaphthalene lactones utilizing DDA reactions of styrene-ynes. The synthetic utility of the DDA reaction is demonstrated by the synthesis of taiwanin C, retrohelioxanthin, justicidin B, isojusticidin B, and their dihydronaphthalene derivatives. Computational methods for chemical shift assignment are presented that allow for regioisomeric lignans to be distinguished.

Ligand-free Ag(I)-catalyzed carboxylative coupling of terminal alkynes, chloride compounds, and CO2

Simple silver(I) slats were found to be highly efficient and selective catalyst for carboxylative coupling of aryl- or alkyl-substituted terminal alkynes, CO2, and various allylic, propargylic or benzylic chlorides to exclusively yield function