81166-84-9Relevant academic research and scientific papers
Ynonylation of Acyl Radicals by Electroinduced Homolysis of 4-Acyl-1,4-dihydropyridines
Luo, Xiaosheng,Wang, Ping
supporting information, p. 4960 - 4965 (2021/07/20)
Herein we report the conversion of 4-Acyl-1,4-dihydropyridines (DHPs) into ynones under electrochemical conditions. The reaction proceeds via the homolysis of acyl-DHP under electron activation. The resulting acyl radicals react with hypervalent iodine(III) reagents to form the target ynones or ynamides in acceptable yields. This mild reaction condition allows wider functionality tolerance that includes halides, carboxylates, or alkenes. The synthetic utility of this methodology is further demonstrated by the late-stage modification of complex molecules.
Photocatalytic Alkylation of Pyrroles and Indoles with α-Diazo Esters
Ciszewski, Lukasz W.,Durka, Jakub,Gryko, Dorota
supporting information, p. 7028 - 7032 (2019/09/12)
This article describes the photoalkylation of electron-rich aromatic compounds with diazo esters. C-2-alkylated indoles and pyrroles are obtained with good yields even though the photocatalyst loading is as low as 0.075 mol %. For EWG-substituted substrates, the addition of a catalytic amount of N,N-dimethyl-4-methoxyaniline is required. Both EWG-EWG- and EWG-EDG-substituted diazo esters are suitable as alkylating agents. The reaction selectivity and mechanistic experiments suggest that carbenes/carbenoid intermediates are not involved in the reaction pathway.
Preparation method for compound containing alkynyl and cyclopropyl
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Paragraph 0024; 0025; 0026; 0027; 0028, (2018/03/07)
The invention relates to the field of organic synthesis, and discloses a preparation method for a compound containing alkynyl and cyclopropyl. The method comprises the following steps: a compound ii with alkyne and alkene is taken as a starting raw material, under effects of a catalyst, the compound ii with the alkyne and the alkene and a diazo substance iv are mixed and reacted in a solvent, andtherefore a reaction liquid containing a compound iii is obtained; and the obtained reaction liquid is added into acid water or hot water for washing, then an inorganic alkali or an organic alkali isadded to adjust the pH to 8-14, and therefore the compound I containing the alkynyl and the cyclopropyl is obtained. The method provided by the invention has the following beneficial effects: 1) the yield of the reaction is improved; 2) the industrialized raw materials used by the method are cheap and easy to obtain; and 3) by-products are reduced, and environmental pollution is reduced.
Potassium tert-Butoxide-Catalyzed Dehydrogenative C-H Silylation of Heteroaromatics: A Combined Experimental and Computational Mechanistic Study
Liu, Wen-Bo,Schuman, David P.,Yang, Yun-Fang,Toutov, Anton A.,Liang, Yong,Klare, Hendrik F. T.,Nesnas, Nasri,Oestreich, Martin,Blackmond, Donna G.,Virgil, Scott C.,Banerjee, Shibdas,Zare, Richard N.,Grubbs, Robert H.,Houk,Stoltz, Brian M.
supporting information, p. 6867 - 6879 (2017/05/31)
We recently reported a new method for the direct dehydrogenative C-H silylation of heteroaromatics utilizing Earth-abundant potassium tert-butoxide. Herein we report a systematic experimental and computational mechanistic investigation of this transformation. Our experimental results are consistent with a radical chain mechanism. A trialkylsilyl radical may be initially generated by homolytic cleavage of a weakened Si-H bond of a hypercoordinated silicon species as detected by IR, or by traces of oxygen which can generate a reactive peroxide by reaction with [KOt-Bu]4 as indicated by density functional theory (DFT) calculations. Radical clock and kinetic isotope experiments support a mechanism in which the C-Si bond is formed through silyl radical addition to the heterocycle followed by subsequent β-hydrogen scission. DFT calculations reveal a reasonable energy profile for a radical mechanism and support the experimentally observed regioselectivity. The silylation reaction is shown to be reversible, with an equilibrium favoring products due to the generation of H2 gas. In situ NMR experiments with deuterated substrates show that H2 is formed by a cross-dehydrogenative mechanism. The stereochemical course at the silicon center was investigated utilizing a 2H-labeled silolane probe; complete scrambling at the silicon center was observed, consistent with a number of possible radical intermediates or hypercoordinate silicates.
Gold(i)-catalyzed dehydrogenative cycloisomerization of 1,5-enynes
Chen, Gen-Qiang,Fang, Wei,Wei, Yin,Tang, Xiang-Ying,Shi, Min
supporting information, p. 10799 - 10802 (2016/09/07)
The gold(i)-catalyzed dehydrogenative cycloisomerization of cyclopropane-tethered 1,5-enynes proceeded smoothly to give multisubstituted benzene derivatives in good to excellent yields. Synthetically important benzocyclobutenes can be produced in high yields in the presence of a gold(i) catalyst and DDQ. Furthermore, this reaction also works very well for non-cyclopropane tethered 1,5-enynes.
2,4-DIOXO-QUINAZOLINE-6-SULFONAMIDE DERIVATIVES AS INHIBITORS OF PARG
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Page/Page column 102; 225; 226, (2016/07/05)
The present invention relates to compounds of formula I that function as inhibitors of PARG (Poly ADP-ribose glycohydrolase) enzyme activity wherein R1a, R1b, R1c, R1d, R1e, W, X1, X2, X3, X4, X5, X6, X7, c are each as defined herein. The present invention also relates to processes for the preparation of these compounds, to pharmaceutical compositions comprising them, and to their use in the treatment of proliferative disorders, such as cancer, as well as other diseases or conditions in which PARG activity is implicated.
Aerobic oxynitration of alkynes with tBuONO and TEMPO
Dutta, Uttam,Maity, Soham,Kancherla, Rajesh,Maiti, Debabrata
supporting information, p. 6302 - 6305 (2015/02/19)
An efficient method for stereoselective nitroaminoxylation of alkyne has been reported. The reaction enjoys a broad substrate scope, good functional group tolerance, and high yields. Synthetically useful α-nitroketones can be accessed through these products in a single step.
Catalyst-dependent divergent synthesis of pyrroles from 3-alkynyl imine derivatives: A noncarbonylative and carbonylative approach
Chen, Gen-Qiang,Zhang, Xiao-Nan,Wei, Yin,Tang, Xiang-Ying,Shi, Min
supporting information, p. 8492 - 8497 (2014/08/18)
A novel Ru0- and RhI-catalyzed noncarbonylative and carbonylative cycloisomerization of readily available 3-alkynyl imine derivatives has been developed to provide 3,4-fused or nonfused pyrrole derivatives efficiently in moderate to
Rhodium-catalyzed carbonylative skeleton rearrangement of 1,4-enynes tethered by a cyclopropane group
Chen, Gen-Qiang,Tang, Xiang-Ying,Shi, Min
supporting information, p. 2311 - 2315 (2015/08/06)
The carbonylative skeleton rearrangement of 1,4 enynes tethered by a cyclopropane group proceeded smoothly in the presence of [Rh(CO)2Cl]2 under CO atmosphere to give the corresponding 1,2,4,5,6,7-hexahydrocyclopenta[a]inden-3(3bH)-o
Gold(I)-catalyzed bis-alkynylation reaction of aromatic aldehydes with alkynylsilanes
Rubial, Belen,Ballesteros, Alfredo,Gonzalez, Jose M.
supporting information, p. 3337 - 3343 (2013/12/04)
The first successful gold(I)-catalyzed reaction of aryl aldehydes with trimethyl(arylethynyl)silanes to furnish bis-alkynylated derivatives is reported. Key C-C bond-forming events involved in the catalytic cycle are analyzed. Copyright
