133033-15-5Relevant articles and documents
Cobalt-Catalyzed Vinylic C-H Addition to Formaldehyde: Synthesis of Butenolides from Acrylic Acids and HCHO
Yu, Shuling,Hong, Chao,Liu, Zhanxiang,Zhang, Yuhong
supporting information, p. 8359 - 8364 (2021/11/01)
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.
Palladium-Catalyzed Asymmetric Hydroesterification of α-Aryl Acrylic Acids to Chiral Substituted Succinates
Ji, Xiaolei,Shen, Chaoren,Tian, Xinxin,Dong, Kaiwu
, p. 8645 - 8649 (2021/10/25)
A palladium-catalyzed asymmetric hydroesterification of α-aryl acrylic acids with CO and alcohol was developed, preparing a variety of chiral α-substituted succinates in moderate yields with high ee values. The kinetic profile of the reaction progress revealed that the alkene substrate first underwent the hydroesterification followed by esterification with alcohol. The origin of the enantioselectivity was elucidated by density functional theory computation.
Enantioselective Enzymatic Reduction of Acrylic Acids
An, Chihui,Shaw, Megan H.,Tharp, Annika,Verma, Deeptak,Li, Hongming,Wang, Heather,Wang, Xiao
supporting information, p. 8320 - 8325 (2020/11/03)
An ene-reductase (ERED 36) with broad substrate specificity was identified, and optimization studies led to the development of an enzymatic protocol for the reduction of α,β-unsaturated acids under mild, aqueous conditions. The substrate scope includes aromatic- A nd aliphatic-substituted acrylic acids, as well as cyclic α,β-substituted acrylic acids, yielding chiral α-substituted acids with exquisite levels of enantioselectivity (>99% ee).
Method for synthesizing alpha-acrylic acid compound by catalyzing carbon dioxide and alkyne with palladium
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Paragraph 0074-0080, (2020/05/02)
The invention belongs to the technical field of organic synthesis, and discloses a method for synthesizing an alpha-acrylic acid compound by catalyzing carbon dioxide and alkyne with palladium. The preparation method comprises the following steps: adding an alkyne compound, a palladium salt catalyst, alkali, a diphosphine ligand, a silane reducing agent and a solvent into a high-pressure reactionkettle, introducing carbon dioxide, stirring and reacting at 60-120 DEG C, washing a reaction liquid with water for extraction, and separating for purification to obtain the alpha-acrylic acid compound. By using the palladium salt as the catalyst and the diphosphine ligand as the ligand, the method has the characteristics of high yield, single selectivity, wide substrate applicability and the like. In addition, by taking the alkyne compound and carbon dioxide as raw materials in the reaction, the method has the advantages as follows: the raw materials are simple and easily available, the operation is simple and convenient and the atom economy is high.
Palladium-Catalyzed Highly Regioselective Hydrocarboxylation of Alkynes with Carbon Dioxide
Chen, Pengquan,Cheng, Ruixiang,Jiang, Huanfeng,Lei, Ming,Lou, Hongming,Qi, Chaorong,Shi, Fuxing,Wang, Lu,Wu, Wanqing,Xiong, Wenfang,Zhu, Baiyao
, p. 7968 - 7978 (2020/08/21)
A Pd-catalyzed highly regioselective hydrocarboxylation of alkynes with carbon dioxide has been established. By the combination of Pd(PPh3)4 and 2,2′-bis(diphenylphosphino)-1,1′-binaphthalene (binap), a variety of functionalized alkynes, including aryl alkynes, aliphatic alkynes, propargylamines, and propargyl ethers, could be leveraged to provide a wide array of α-acrylic acids in high yields with high regioselectivity under mild reaction conditions. Experimental and DFT mechanistic studies revealed that this reaction proceeded via the cyclopalladation process of alkynes and carbon dioxide in the presence of binap to generate a five-membered palladalactone intermediate and enabled the formation of Markovnikov adducts. Moreover, this strategy provided an effective method for the late-stage functionalization of alkyne-containing complicated molecules, including natural products and pharmaceuticals.
Efficient Synthesis of Spirooxindole Pyrrolones by a Rhodium(III)-Catalyzed C?H Activation/Carbene Insertion/Lossen Rearrangement Sequence
Ma, Biao,Wu, Peng,Wang, Xing,Wang, Zhengyu,Lin, Hai-Xia,Dai, Hui-Xiong
supporting information, p. 13335 - 13339 (2019/08/20)
A rhodium(III)-catalyzed domino annulation of simple olefins with diazo oxindoles to give spirooxindole pyrrolone products is described. This reaction can be formally viewed as the result of an anomalous tandem C?H activation, carbene insertion, Lossen rearrangement, and a nucleophilic addition process. The potential utility of this reaction was further demonstrated by the late-stage diversification of drug molecules.
Ruthenium-Catalyzed C-H Allylation of Alkenes with Allyl Alcohols via C-H Bond Activation in Aqueous Solution
Wu, Xiaowei,Ji, Haitao
, p. 12094 - 12102 (2018/10/02)
A robust Ru(II)-catalyzed C-H allylation of electron-deficient alkenes with allyl alcohols in aqueous solution is reported. This method provides a straightforward and efficient access to the synthetically useful 1,4-diene skeletons. With the assistance of the N-methoxycarbamoyl directing group, this allylation reaction features a broad substrate scope with good functional group tolerance, excellent regio- and stereoselectivity, absence of metal oxidants, water-tolerant solvents, and mild reaction conditions. The mechanistic studies indicate that the process of the reversible C-H bond ruthenation is assisted by acetate, and the rate-determining step is unlikely to be the step of C-H bond cleavage.
Asymmetric Hydrogenation of α-Substituted Acrylic Acids Catalyzed by a Ruthenocenyl Phosphino-oxazoline-Ruthenium Complex
Li, Jing,Shen, Jiefeng,Xia, Chao,Wang, Yanzhao,Liu, Delong,Zhang, Wanbin
, p. 2122 - 2125 (2016/06/01)
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.
Cs2CO3-promoted carboxylation of N-tosylhydrazones with carbon dioxide toward α-arylacrylic acids
Sun, Song,Yu, Jin-Tao,Jiang, Yan,Cheng, Jiang
, p. 2855 - 2860 (2015/03/18)
A Cs2CO3-promoted carboxylation of N-tosylhydrazones and CO2 has been developed. The reaction proceeded efficiently at 80 C under atmospheric CO2, gave the corresponding α-arylacrylic acids in moderate to good yields. This method was featured with (1) the employment of Cs2CO3 rather than nBuLi as the base; (2) a reaction temperature of 80 C rather than -78 C.
Directing-group-assisted copper-catalyzed olefinic trifluoromethylation of electron-deficient alkenes
Feng, Chao,Loh, Teck-Peng
, p. 122414 - 122417 (2013/12/04)
Assistance provided: The directing group in the title reaction not only activates the substrates but also allows the stereospecific formation of cis-trifluoromethylated products. The reaction is operationally simple and tolerates a wide variety of functional groups, thus providing an efficient method for the stereoselective synthesis of β-CF3-functionalized acrylamide derivatives. Copyright
