- Rhodium-Catalyzed Carbonylative Coupling of Alkyl Halides with Phenols under Low CO Pressure
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A rhodium-catalyzed carbonylative transformation of alkyl halides under low pressure of CO has been developed. This robust catalyst system allows using phenols as the carbonylative coupling partner and, meanwhile, exhibits high functional group tolerance and good chemoselectivity. Substrates even with a large steric hindrance group or multiple reaction sites can be selectively converted into the desired products in good to excellent yields. A gram-scale experiment was performed and delivered an almost quantitative amount of the product. Control experiments were performed as well, and a possible reaction mechanism is proposed.
- Ai, Han-Jun,Li, Chong-Liang,Wang, Hai,Wu, Xiao-Feng
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p. 5147 - 5152
(2020/05/27)
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- CARBOXYLIC ACID ESTER PRODUCTION METHOD
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Provided is a production method whereby corresponding carboxylic acid esters can be obtained from a variety of carboxylic acids at a high yield, even under conditions using a simple reaction operation and little catalyst and even if the amount of substrate used is theoretical. A production method for carboxylic acid ester, whereby a prescribed diester dicarbonate, carboxylic acid, and alcohol are reacted in the presence of at least one type of magnesium compound and at least one type of alkali metal compound.
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Paragraph 0075; 0076
(2019/01/04)
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- Metal-Free O-Arylation of Carboxylic Acid by Active Diaryliodonium(III) Intermediates Generated in situ from Iodosoarenes
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The metal-free arylative coupling of carboxylic acids using iodosoarenes without the use of a catalyst and base, which is applicable to even a highly-polar molecule bearing multiple alcohol groups, is reported. The in situ preparation of the reactive diaryliodonium(III) carboxylates is the important key to this approach, and the introduction of the trimethoxybenzene auxiliary enables both the smooth salt formations and the selective aryl transfer events during the couplings. (Figure presented.).
- Dohi, Toshifumi,Koseki, Daichi,Sumida, Kohei,Okada, Kana,Mizuno, Serina,Kato, Asami,Morimoto, Koji,Kita, Yasuyuki
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p. 3503 - 3508
(2017/09/13)
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- METHOD FOR PRODUCING CARBOXYLIC ESTER
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PROBLEM TO BE SOLVED: To provide a method that can efficiently produce carboxylic ester even with a small amount of use of catalysts at room temperature and normal pressure (25°C, 1 atm). SOLUTION: This invention relates to a method for producing carboxylic ester by the reaction between a compound represented by the following formula (I), carboxylic acid anhydride and alcohol, the reaction to occur in the presence of at least one Group I metal compound and at least one Group II metal compound [in formula (I), R1 and R2 are a C1-C20 hydrocarbon group]. SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT
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Paragraph 0059; 0060
(2018/04/18)
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- METHOD FOR PRODUCING CARBOXYLIC ACID ANHYDRIDE AND METHOD FOR PRODUCING CARBOXYLIC ACID ESTER
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Provided is a production method whereby corresponding carboxylic acid anhydrides and carboxylic acid esters can be obtained at high yield from various carboxylic acids even without a solvent and near room temperature. A method for producing a carboxylic acid anhydride represented by formula (II), the method comprising reacting a compound represented by formula (I) and a carboxylic acid in the presence of a Group II metal compound having an ionic ligand containing an oxygen atom. A method for producing a carboxylic acid ester, the method comprising reacting a carboxylic acid anhydride produced by the aforementioned method and an alcohol. In formula (I), R1 represents a C1-20 hydrocarbon group. In formula (II), R2 represents a C1-20 hydrocarbon group.
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Paragraph 0090
(2017/04/18)
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- Pd-Catalyzed Regiodivergent Hydroesterification of Aryl Olefins with Phenyl Formate
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An effective Pd-catalyzed regiodivergent hydroesterification of aryl olefins with phenyl formate is described. Either linear or branched phenyl arylpropanoates can be obtained in good yields with high regioselectivities by the judicious choice of ligand without the use of toxic CO gas.
- Ren, Wenlong,Chang, Wenju,Wang, Yang,Li, Jingfu,Shi, Yian
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supporting information
p. 3544 - 3547
(2015/07/28)
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- Comparisons of O-acylation and Friedel-Crafts acylation of phenols and acyl chlorides and Fries rearrangement of phenyl esters in trifluoromethanesulfonic acid: Effective synthesis of optically active homotyrosines
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Reactions involving phenol derivatives and acyl chlorides have to be controlled for competitive O-acylations and C-acylations (Friedel-Crafts acylations and Fries rearrangements) in acidic condition. The extent for these reactions in trifluoromethanesulfonic acid (TfOH), which is used as catalyst and solvent, is examined. Although diluted TfOH was needed for effective O-acylation, concentrated TfOH was required for effective C-acylations in mild condition. These results have been applied to the novel synthesis of homotyrosine derivatives. Both Fries rearrangement of N-TFA-Asp(OBn)-OMe and Friedel-Crafts acylation of phenol with N-TFA-Asp(Cl)-OMe in TfOH afforded the homotyrosine skeleton, followed by reduction and deprotection afforded homotyrosines maintaining stereochemistry of Asp as an optically pure form.
- Murashige, Ryo,Hayashi, Yuka,Ohmori, Syo,Torii, Ayuko,Aizu, Yoko,Muto, Yasuyuki,Murai, Yuta,Oda, Yuji,Hashimoto, Makoto
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experimental part
p. 641 - 649
(2011/03/19)
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- Highly selective reaction of α-halo-αβ-unsaturated esters with ketones or aldehydes promoted by SmI2: An efficient alternative access to Baylis-Hillman adducts
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A samarium diiodide promoted addition of aromatic or aliphatic β-substituted-α-halo-α,β-unsaturated esters 1 or 3 to both ketones (in THF) and aldehydes (in acetonitrile) led to (Z)-2-(1-hydroxyalkyl)- 2,3-alkenoates 2 and 4 in good yields and very high stereoselectivity. This method constitutes an efficient and valuable alternative to the synthesis of Baylis-Hillman adducts. A mechanism is proposed to explain this transformation.
- Concellon, Jose M.,Huerta, Monica
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p. 4714 - 4719
(2007/10/03)
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- Cytotoxicity and antiestrogenicity of a novel series of basic diphenylethylenes
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On the premise that it is necessary to develop antiestrogens with a higher cytotoxic component in order to reduce the risks of the development of heterogeneous malignant cell populations in breast cancer, we studied a novel series of basic diphenylethylenes, for the most part devoid of estrogenic activity, with low antiestrogenicity but much enhanced cytotoxicity compared to the reference drug tamoxifen. The main structural features associated with cytotoxicity were E isomery, substituents of five to eight carbons on the ethylene bond, and dibasicity.
- Gilbert, Jacques,Fuentes, Maryse,Ojasoo, Tiiu,Doré, Jean-Christophe,Pons, Michel
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p. 1104 - 1111
(2007/10/03)
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- Method of preparing acyloxybenzenesulfonic acids and salts thereof
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Alkali metal salts and alkaline earth metal salts of acyloxybenzenesulfonate are prepared by sulfonating an aryl ester of an organic acid with gaseous sulfur trioxide to produce a sulfonation reaction mixture containing acyloxybenzenesulfonic acid, neutralizing the sulfonation reaction mixture with alkali metal hydroxide or alkaline earth metal hydroxide to produce an alkali metal salt or alkaline earth metal salt of an acyloxybenzenesulfonic acid and thereafter recovering from the reaction mixture the acyloxybenzenesulfonic acid salt product thus formed.
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- Alkanoyloxybenzenesulfonate salt production
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An alkali metal or an alkaline earth metal salt of an acyloxybenzenesulfonate of the formula: STR1 wherein R is a hydrocarbyl group containing up to 30 carbon atoms selected from alkyl, alkenyl, cycloalkyl, aryl, aralkyl and M is an alkali metal or an alk
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