854545-61-2Relevant academic research and scientific papers
Piperidine promoted aldol reaction of alkynyl aldehydes and ethyl diazoacetate
Zhang, Guifu,Sun, Sheng,Jiang, Longqiang,Sun, Shaofa,Luo, Xing,Chen, Zhi,Guo, Haibing,Xing, Yalan
, p. 649 - 651 (2017)
Complex diazo compounds containing propargyl alcohol functional group were prepared by an efficient aldol reaction of alkynyl aldehydes and ethyl diazoacetate in good yields. Piperidine was utilized as a base to catalyze this transformation. The aldol reaction showed broad substrate scopes and good functional group compatibility.
Synthesis method of 3-hydroxyl diazoester intermediate alkyne compound
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Paragraph 0026; 0027; 0028, (2016/12/22)
The invention provides a synthesis method of a 3-hydroxyl diazoester intermediate alkyne compound. The synthesis method comprises the following steps: with a diazoacetate compound and various kinds of substituted propiolaldehyde as raw materials, synthesizing the 3-hydroxyl diazoester intermediate alkyne compound in a mild alkaline environment. The synthesis method provided by the invention has the advantages of simple operation, mild reaction conditions, cheap and available raw materials, wide reaction substrate adaptability, high product selectivity and yield, environmental friendliness and the like and has a good industrial application prospect.
Wolff rearrangement of β-alkynyl-α-diazo-β-ketoesters: Light-induced acetylene-allene isomerization and its use for activation of enediynes
Zhegalova, Natalia G.,Popik, Vladimir V.
, p. 969 - 975 (2012/01/13)
Irradiation of β-phenylethynyl-α-diazo-β-ketoester with 300 or 350nm light results in efficient and regioselective Wolff rearrangement producing only the product of alkynyl group migration. Addition of alcohols to the resulting α-oxoketene yields α-phenylethynyl-β-diester, which undergoes rapid (τ1min) tautomerization to 1,1-dicarbalkoxyallene. The latter then adds second molecule of alcohol in Michael fashion to form the final product, 2-(1-alkoxy-2-phenylvinyl)malonic ester. α-Phenylethynyl- β-ketoacid produced from the ketene in aqueous solutions does not isomerize to an allene but rather undergoes decarboxylation to give β,γ- acetylenic ester. Introduction of o-(3-hydroxy-1-propynyl) fragment in the structure of the parent α-diazo-β-ketoester allowed us to achieve two goals simultaneously: ring closure by intramolecular nucleophilic attack of propargyl alcohol on photo-generated ketene and the subsequent acetylene-allene rearrangement. The resulting enyne-allene undergoes spontaneous Myers-Saito cycloaromatization generating 1,4-biradical. In alcohol solutions, however, ketene reaction with solvent outcompetes the intramolecular process.
DBU-catalyzed condensation of acyldiazomethanes to aldehydes in water and a new approach to ethyl β-hydroxy α-arylacrylates
Xiao, Fengping,Liu, Yu,Wang, Jianbo
, p. 1147 - 1149 (2007/10/03)
DBU-catalyzed condensation of ethyl diazoacetate (EDA) with aldehydes in pure water afforded corresponding β-hydroxy α-diazo carbonyl compounds. The β-hydroxy group of the products was further converted into β-siloxy group. The Rh(II)-catalyzed reaction of the β-aryl β-siloxy α-diazo carbonyl compounds gave 1,2-aryl shift products predominantly. The three-step transformation constitutes an efficient synthesis of ethyl β-hydroxy α-arylacrylates.
A new method for the synthesis of 2-cyclopenten-1-one-5-carboxylic ester derivatives via Rh2(OAc)4-mediated intramolecular C-H insertion reaction of 4Z-β-vinyl-α-diazo β-ketoesters
Deng, Guisheng,Xu, Baihua,Wang, Jianbo
, p. 10811 - 10817 (2007/10/03)
2-Cyclopenten-1-one-5-carboxylic ester derivatives 14 are synthesized in a four-step-reaction sequence starting from alkynyl aldehydes 9 via 4Z-β-vinyl-α-diazo β-ketoesters intermediate 8. The synthetic method for 8 is described. When the δ substituent is
