107473-99-4

Upstream product

• 53088-68-9 methyl 3-chlorophenylacetate 
• 64-18-6 formic acid 
• 766-83-6 m-chlorophenylacetylene 
• 62123-73-3 ethyl 2‐(3‐chlorophenyl)‐2‐oxoacetate 
• 1101067-22-4 ethyl 2-(3-chlorophenyl)acrylate 

Downstream Products

• 103040-42-2 (S)-methyl 2-(3-chlorophenyl)propanoate 
• 14161-84-3 (S)-(+)-2-(3'-chlorophenyl)propanoic acid 
• 1174749-44-0 (S)-3-(3-chlorophenyl)-1,3-dimethylindolin-2-one 
• 41904-39-6 3-chloro-benzeneacetyl chloride 
• 1325755-57-4 tert-butyl (4S)-4-(3-chlorophenyl)-4-[(3,5-dimethyl-1H-pyrazol-1-yl)carbonyl]cyclopent-1-ene-1-carboxylate 
• 1325755-39-2 C₁₄H₁₃ClN₂O 

Relevant academic research and scientific papers

Nickel-catalyzed hydrocarboxylation of alkynes with formic acid

A protocol for nickel-catalyzed hydrocarboxylation of alkynes with formic acid was developed. The protocol allowed for highly efficient synthesis of acrylic acid with a TON of up to 7700.

Hydrocarboxylation of alkynes with formic acid over multifunctional ligand modified Pd-catalyst with co-catalytic effect

Hydrocarboxylation of terminal alkynes with formic acid (FA) was accomplished over a multifunctional ligand (L2) modified Pd-catalyst, advantageous with 100% atom-economy, free use of CO and H2O, mild reaction conditions, and high yields (56–89%) of α,β-unsaturated carboxylic acids with 100% regioselectivity to the branched ones. The multifunctional ligand of L2 as a zwitterion salt containing the phosphino-fragment (-PPh2), Lewis acidic phosphonium cation and sulfonate group (-SO3?), was constructed on the skeleton of 1.1′-binaphthyl-2.2′-diphenyl phosphine (BINAP) upon selective quaternization by 1,3-propanesultone. It was found that L2 conferred to the Pd-catalyst the co-catalytic effect, wherein the phosphino-coordinated Pd-complex was responsible for activation of all the substrates (including CO, FA and alkyne), and the incorporated phosphonium cation was responsible for synergetic activation of FA. The 1H NMR spectroscopic analysis supported that FA was truly activated by the incorporated Lewis acidic phosphonium cation in L2 via “acid-base pair” interaction. The in situ FT-IR spectra demonstrated that, the presence of Ac2O and NaOAc additives in the catalytic amount could dramatically promote the in situ release of CO from FA, which was required to initiate the hydrocarboxylation.

Synthesis of Cyclopentenones through Rhodium-Catalyzed C-H Annulation of Acrylic Acids with Formaldehyde and Malonates

An efficient rhodium-catalyzed protocol for the synthesis of cyclopentenones based on a three-component reaction of acrylic acids, formaldehyde, and malonates via vinylic C-H activation is reported. Exploratory studies showed that 5-alkylation of as-prepared cyclopentenones could be realized smoothly by the treatment of a variety of alkyl halides with a Na2CO3/MeOH solution. Excess formaldehyde and malonate led to a multicomponent reaction that afforded the multisubstituted cyclopentenones through a Michael addition.

Cobalt-Catalyzed Vinylic C-H Addition to Formaldehyde: Synthesis of Butenolides from Acrylic Acids and HCHO

A carboxyl-assisted C-H functionalization of acrylic acids with formaldehyde to give butenolides is described. It is the first time that the addition of an inert vinylic C-H bond to formaldehyde has been achieved via cobalt-catalyzed C-H activation. The unique reactivity of the cobalt species was observed when compared with related Rh or Ir catalysts. γ-Hydroxymethylated butenolides were produced by the treatment of Na2CO3 after the catalytic reaction in one pot.

3,3′-Disubstituted Oxindoles Formation via Copper-Catalyzed Arylboration and Arylsilylation of Alkenes

Arylboration and arylsilylation reactions of N-(2-iodoaryl)acrylamides with bis(pinacolato)-diboron (B2pin2) or PhMe2Si-Bpin are developed by using simple CuOAc as the sole catalyst. A range of boron-or silane-bearing 3,3′-disubstituted oxindoles are obtained in moderate to excellent yields. The reaction is proposed to proceed via a domino sequence involving intermolecular olefin borylcupration or silylcupration followed by intramolecular coupling of an alkyl-Cu intermediate with aryl iodide.

Palladium-catalyzed intermolecular C-H silylation initiated by aminopalladation

A Pd(ii)-catalyzed intermolecular C-H silylation reaction initiated by aminopalladation has been developed. The C-H bonds were activated by an alkyl Pd(ii) species generated through aminopalladation and then disilylated with hexamethyldisilane to form disilylated indolines as the final products. The reaction provides a new method for the introduction of silyl groups into complex organic molecules.

Enantioselective Construction of Quaternary All-Carbon Centers via Copper-Catalyzed Arylation of Tertiary Carbon-Centered Radicals

An enantioselective copper-catalyzed arylation of tertiary carbon-centered radicals, leading to quaternary all-carbon stereocenters, has been developed herein. The tertiary carbon-centered radicals, including both benzylic and nonbenzylic radicals, were produced by the addition of trifluoromethyl radical to α-substituted acrylamides, and subsequently captured by chiral aryl copper(II) species to give C-Ar bonds with excellent enantioselectivity. Importantly, an acylamidyl (CONHAr) group adjacent to the tertiary carbon radical is essential for the asymmetric radical coupling. The reaction itself features broad substrate scope, excellent functional group compatibility and mild conditions.

Water as a Hydride Source in Palladium-Catalyzed Enantioselective Reductive Heck Reactions

Pd-catalyzed intramolecular asymmetric carbopalladation of N-aryl acrylamides followed by reduction of C(sp3)-Pd intermediate using diboron–water as a hydride source afforded enantioenriched 3,3-disubstituted oxindoles in high yields and enantioselectivities. When heavy water was used as a deuterium donor in combination with bis(catecholato)diboron (Cat2B2), deuterium was incorporated into the products with high synthetic efficiency. The ligand determined both the enantioselectivity of the reaction and the reaction pathways, thereby affording either hydroarylation (reductive Heck) or carboborylation products.

Asymmetric Hydrogenation of α-Substituted Acrylic Acids Catalyzed by a Ruthenocenyl Phosphino-oxazoline-Ruthenium Complex

Asymmetric hydrogenation of various α-substituted acrylic acids was carried out using RuPHOX-Ru as a chiral catalyst under 5 bar H2, affording the corresponding chiral α-substituted propanic acids in up to 99% yield and 99.9% ee. The reaction could be performed on a gram-scale with a relatively low catalyst loading (up to 5000 S/C), and the resulting product (97%, 99.3% ee) can be used as a key intermediate to construct bioactive chiral molecules. The asymmetric protocol was successfully applied to an asymmetric synthesis of dihydroartemisinic acid, a key intermediate required for the industrial synthesis of the antimalarial drug artemisinin.

Method for synthesizing alpha, beta-unsaturated acid by using formic acid and alkine

The invention relates to a method for synthesizing alpha, beta-unsaturated acid by using formic acid and alkine, in particular to a method for synthesizing alpha, beta-unsaturated acid by using formic acid and alkine under the effect of a nickel catalyst. The consumption of the catalyst is 0.01 to 2 mol percent of the quantity of a substrate substance; the consumption of estolide is 3 to 30 mol percent of the quantity of the substrate substance; the pressure of acetylene gas is 1 to 10 MPa; the reaction temperature is 25 to 100 DEG C; the reaction time is 5 to 12 hours. The method has the advantages that the existing alkine hydrocarboxylation defects are overcome; the use of toxic carbon monoxide gas does not needed; the reaction conditions of the whole process are mild; the efficiency is high; the selectivity is good; the method belongs to a method for preparing the alpha, beta-unsaturated acid with the advantages that the method conforms to green chemistry and has good application aspects; good industrial application prospects are realized.