26197-64-8

Upstream product

• 5707-59-5 2-benzyl-crotonic acid 
• 994-52-5 butyric acid silicic acid-anhydride 
• 100-52-7 benzaldehyde 
• 156-54-7 sodium butyrate 
• 105-54-4 butanoic acid ethyl ester 
• 80-58-0 2-Bromobutyric acid 
• 105-58-8 Diethyl carbonate 
• 622-29-7 N-Benzylidenemethylamine 
• 601-75-2 ethylmalonic acid 
• 64-17-5 ethanol 
• 64-18-6 formic acid 
• 622-76-4 1-phenyl-1-butyne 
• 60754-33-8 (E)-ethyl 2-benzylidenebutanoate 
• 97-94-9 triethyl borane 

Downstream Products

• 77945-07-4 2-ethyl-3t-phenyl-acrylic acid-(2-diethylamino-ethyl ester) 
• 88153-39-3 (Z)-2-benzylidenebutanoic acid 
• 99853-87-9 (E)-2-benzylidenebutanoyl chloride 
• 3571-78-6 2,4-Dioxo-5-ethyl-6-phenyl-tetrahydro-1,3-thiazin 

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.

Copper-Photocatalyzed Contra-Thermodynamic Isomerization of Polarized Alkenes

The contra-thermodynamic isomerization of α- and β-substituted cinnamate derivatives catalyzed by the Cu(OAc)2/rac-BINAP complex under blue light irradiation is reported. The use of an oxazolidinone template, which favored the complexation of the copper catalyst to the substrate, allowed the E → Z isomerization of the catalytically formed chromophore under simple and robust reaction conditions in good to excellent ratios. The mechanism of this process based on the transient formation of a chromophore was also studied.

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

Copper-Catalyzed Stereodefined Construction of Acrylic Acid Derivatives from Terminal Alkynes via CO2 Insertion

IPrCuCl catalyzes the CO2 insertion reaction undergone by a dialkylvinylborane intermediate derived from alkynyltrialkylborate by a 1,2-alkyl group migration to afford α-alkyl acrylic acids with excellent regio- and stereoselectivities.

Novel and practical asymmetric synthesis of β2,3-amino esters using asymmetric Michael addition of chiral amine

A practical method for the synthesis of chiral β2,3-amino esters having various substituents was developed, which is characterized by an asymmetric Michael addition reaction of a chiral lithium amide with trisubstituted (E)-α,β-unsaturated esters. We found that a highly face-selective protonation occurred by the quick addition of water to the enolate intermediate derived from the Michael addition reaction to afford N-protected β2,3-amino esters in moderate to excellent yields. This finding was made possible by the facile preparation of geometrically pure trisubstituted (E)-α,β-unsaturated esters, which was established recently by our group. The subsequent deprotection of the amino group in the Michael adduct by using N-iodosuccinimide (NIS) efficiently provided β2,3-amino esters having various substituents.

Ni-Catalyzed Regioselective Hydrocarboxylation of Alkynes with CO2 by Using Simple Alcohols as Proton Sources

A mild and user-friendly Ni-catalyzed regioselective hydrocarboxylation of alkynes with CO2 (1 bar) is described. This protocol is characterized by a wide scope while obviating the need for sensitive organometallic species and by an unprecedented regioselectivity pattern using simple alcohols as proton sources.

Reactivity of substituted and unsubstituted diphenylphosphonium diylides towards carbonic acids derivatives

In order to further delimit the scope of application of diphenylphosphonium diylides, their reactivity towards carbonic acid derivatives was investigated. Non-stabilized diylides react with ethyl carbonate to give new monoylide intermediates which lead, by in situ Wittig reaction with carbonyl compounds, to the synthesis of α,β-unsaturated esters or acids the double bond being di- or trisubstituted. The reaction proceeds in mild conditions and with high E stereoselectivity. Stabilized diylides are inactive towards carbonates but semi-stabilized diylides react with ethyl carbonate leading to the synthesis of non-functionalized alkenes instead of the α,β-unsaturated esters or acids.

α-LITHIOALKYLPHOSPHONATES AS FUNCTIONAL GROUP CARRIERS. PART II. A DIRECT (E)-CINNAMIC AND 2-ALKYL-CINNAMIC ACIDS SYNTHESIS.

Sequential treatment of α-lithioalkylphosphonates with tert-butyl fluoroformate or di-tert-butyl dicarbonate and an aromatic aldehyde gives tert-butyl acrylic esters convertible into acrylic acids by protolysis with trifluoroacetic acid.

Phosphite-Mediated in Situ Carboxyvinylation: A New General Acrylic Acid Synthesis

Sequential treatment of a 2-halo carboxylic acid with a dialkyl phosphite and an aldehyde or ketone in the presence of 3 equiv of sodium hydride in glyme constitutes a new general acrylic acid synthesis superior to conventional methods.An alkoxide-in-alcohol variant may be used with bromo- or chloroacetic acid and aryl aldehydes to produce cinnamic acids conveniently.The scope and other features of the synthesis are discussed.