3127-88-6

Upstream product

• 103-82-2 phenylacetic acid 
• 123-38-6 propionaldehyde 
• 64-18-6 formic acid 
• 622-76-4 1-phenyl-1-butyne 
• 124-38-9 carbon dioxide 
• 70982-84-2 trans-4-Ethyl-3-phenyl-2-oxetanon 

Relevant academic research and scientific papers

The synergistic copper/ppm Pd-catalyzed hydrocarboxylation of alkynes with formic acid as a CO surrogate as well as a hydrogen source: An alternative indirect utilization of CO2

An unprecedented strategy has been developed involving the earth-abundant Cu-catalyzed hydrocarboxylation of alkynes with HCOOH to (E)-acrylic derivatives with high regio- and stereoselectivity via synergistic effects with ppm levels of a Pd catalyst. Both symmetrical and unsymmetrical alkynes bearing various functional groups were successfully hydrocarboxylated with HCOOH, and the modification of a pharmaceutical molecule exemplified the practicability of this process. This protocol employs HCOOH as both a CO surrogate and hydrogen donor with 100% atom economy and it can be viewed as an alternative approach for indirect CO2 utilization. Mechanistic investigations indicate a Cu/ppm Pd cooperative catalysis mechanism via alkenylcopper species as potential intermediates formed from Cu-hydride active catalytic species with HCOOH as a hydrogen source. This bimetallic system involving inexpensive Cu and trace Pd provides a reliable and efficient hydrocarboxylation method to access industrially useful acrylic derivatives with HCOOH as a hydrogen source, and it provides novel clues for optimizing other Cu-H-related co-catalytic systems.

Method for preparing alpha, beta-unsaturated carboxylic acid compound

The invention discloses a method for preparing an alpha, beta-unsaturated carboxylic acid compound, which comprises the following steps: 1) in an atmosphere containing carbon dioxide, heating and reacting a mixture containing hydrosilane and a copper catalyst to obtain a system I; and 2) adding a raw material containing alkyne and a nickel catalyst into the system I in the step 1), and heating to react. The method has the advantages of simple, easily available, cheap and stable raw materials, common, easily available and stable catalyst, mild reaction conditions, simple post-treatment, high yield and the like.

Discovery of Oxygen α-Nucleophilic Addition to α,β-Unsaturated Amides Catalyzed by Redox-Neutral Organic Photoreductant

The conjugate additions of oxygen-centered nucleophiles to conjugate acceptors are among the most powerful C-O bond formation reactions. The conjugate addition normally takes place at the β-position carbon to the electron-withdrawing group, resulting in the formation of a stabilized carbanion intermediate that can be quenched by proton or electrophiles to form the β-addition (i.e., hetero-Michael addition) products. On the contrary, the formation of α-hydroxyl or alkoxyl amides through conjugate addition needs an α,β-inverse addition. Nevertheless, a regio-inversed nucleophilic α-addition of oxygen-centered nucleophiles to α,β-unsaturated carbonyl compounds still remains less explored because of the electronic mismatch. In this research, we discovered the first α-specific nucleophilic addition of α,β-unsaturated amides with oxygen and fluoride nucleophiles. This region-inversed nucleophilic addition is enabled by the catalysis of a novel redox-neutral nondonor-acceptor organic photoreductant (CBZ6). As low as 0.5 mol % of visible light photoreductant was employed. The mechanistic insights were also explored. The oxidative potential of the excited state of CBZ6 is obtained in -1.92 V (vs SCE), presenting a stronger reductive potential than representative metal-cored or organic photoredox catalysts. This feature enabled the umpolung of α,β-unsaturated amides to take place α-nucleophilic addition other than the normal β-addition.

Cp2TiCl2-catalyzed hydrocarboxylation of alkynes with CO2: formation of α,β-unsaturated carboxylic acids

Cp2TiCl2-catalyzed hydrocarboxylation of alkynes with CO2 (atmospheric pressure) has been reported. A range of alkynes were transformed to the corresponding α,β-unsaturated carboxylic acids in high yields with high regioselectivity. The reaction proceeded with hydrotitanation, transmetalation, and subsequently carboxylation with CO2

Structural Effects of the Acidity of E-α-Phenyl-β-arylacrilic Acids

The dissociation equilibrium constants of some E-α-phenyl-β-arylacrilic acids (Ar=2-pyridyl, 3-pyridyl, 4-pyridyl, 1-naphthyl, 2-naphthyl, anthracen-9-yl) have been measured in 80percent aqeous 2-methoxyethanol at 25 deg C., The pKa values of these acids, together with those of p-substituted phenyl, 2-furyl, 2-thienyl and selenophen-2-yl derivitives, have been rationalized by an equation involving separate contributions of polar, conjugative and steric effects of heterocycles.The pKa values of some E-α-phenyl-β-alkylacrilic acids (alk=methyl; ethyl; n-propyl; i-propyl; n-butyl; i-butyl) are also reported.