3760-10-9Relevant academic research and scientific papers
Co-catalysis over a tri-functional ligand modified Pd-catalyst for hydroxycarbonylation of terminal alkynes towards α,β-unsaturated carboxylic acids
Yang, Da,Liu, Huan,Liu, Lei,Guo, Wen-Di,Lu, Yong,Liu, Ye
, p. 5336 - 5344 (2019/10/11)
An amphiphilic tri-functional ligand (L1) containing a Lewis acidic phosphonium cation, a phosphino-fragment and a hydrophilic sulfonate anion (-SO3-) enabled Pd(OAc)2 to efficiently co-catalyze the hydroxycarbonylation of terminal alkynes towards α,β-unsaturated carboxylic acids. These incorporated functional groups synergistically promoted the reaction, which proved more effective than the ligands lacking -SO3- and/or phosphonium and the mechanical mixtures of the individual functional groups independently. The molecular structure of Pd-L1 indicated that -SO3- in L1 served as a secondary O-donor ligand with reversible coordinating ability, cooperating with the phosphino-fragment to stabilize the Pd-catalyst. The in situ FT-IR analysis verified that the formation and stability of Pd-H active species in charge of hydroxycarbonylation were dramatically facilitated by the presence of L1. It was believed that, over the L1-based Pd-catalyst, H2O was cooperatively activated by the Lewis acidic phosphonium via "acid-base pair" interaction (H2O → P(v)+) and by the hydrophilic SO3-via hydrogen bonding (SO3-?H2O), giving rise to the formation of dimeric and mono-nuclear Pd-H species driven by reversible SO3--coordination. In addition, the L1-based Pd-catalyst could be immobilized in the ionic liquid [Bmim]NTf2 for six-run recycling uses without obvious activity loss and detectable metal leaching.
Method for synthesizing alpha, beta-unsaturated acid by using formic acid and alkine
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Paragraph 0024, (2016/10/27)
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.
Nickel-catalyzed hydrocarboxylation of alkynes with formic acid
Hou, Jing,Yuan, Ming-Lei,Xie, Jian-Hua,Zhou, Qi-Lin
supporting information, p. 2981 - 2984 (2016/06/06)
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.
Stereoselective synthesis of α,β-unsaturated carboxylic acids from alkynes using the Fe(CO)5/t-BuOK/AcOH/CH2Cl 2 reagent system
Beesu, Mallesh,Periasamy, Mariappan
experimental part, p. 30 - 33 (2012/04/17)
Reactive iron carbonyl species generated in situ using the Fe(CO) 5/t-BuOK/CH3COOH/CH2Cl2 reagent system reacts with alkynes to give the corresponding α,β-unsaturated carboxylic acids after CuCl2·2H2O oxidation with some regio and stereoselectivity.
Nickel-mediated regio- and chemoselective carboxylation of alkynes in the presence of carbon dioxide
Saito, Shinichi,Nakagawa, Satomi,Koizumi, Toru,Hirayama, Kyoko,Yamamoto, Yoshinori
, p. 3975 - 3978 (2007/10/03)
Alkynes are carboxylated in a highly regio- and chemoselective manner in the presence of Ni(cod)2, DBU, and CO2 to give the carboxylated products in good yields. The reaction was carried out under very mild conditions (CO2 1 atm, 0°C) in the presence of a stoichiometric amount of alkynes, conjugated enynes, or diynes. The high selectivity observed in the reaction would be explained in terms of the stability and the reactivity of the intermediates.
Ligand-directed reaction products in the nickel-catalyzed electrochemical carboxylation of terminal alkynes
Labbe, Eric,Dunach, Elisabet,Perichon, Jacques
, p. C51 - C56 (2007/10/02)
The influence of a series of N and P ligands in the nickel-catalyzed electrochemical carboxylation of 1-octyne has been studied.Different carboxylic acids are obtained depending on the nature of the ancillary ligand, and results afford an example of high ligand-directed product specificity.
Electrochemical carboxylation of terminal alkynes catalyzed by nickel complexes: unusual regioselectivity
Dunach, Elisabet,Perichon, Jacques
, p. 239 - 246 (2007/10/02)
The electrochemical reduction of the nickel(II) complex Ni(bipy)3(BF4)2 yields an active catalyst for the regioselective functionalization of the 2-position of terminal alkynes with carbon dioxide.A series of α-substituted acrylic acids have been obtained with selectivities of 65-90percent and fair overall yields.
