37434-59-6Relevant academic research and scientific papers
Reactions of dimethoxycarbene with carbon-sulfur double bonds
Dawid, Malgorzata,Reid, Darren L.,Warkentin, John,Mloston, Grzegorz
, p. 86 - 89 (2005)
Unlike electrophilic carbenes, which react at sulfur to produce thiocarbonyl ylide intermediates, dimethoxycarbene (DMC), generated by thermolysis of an oxadiazoline at 110°C in benzene in a sealed tube, reacts at carbon, possibly to generate a zwitterionic intermediate, or at both carbon and sulfur in a concerted process that generates a thiirane. In case of the strained 2,2,4,4-tetramethylcyclobutane-1,3-dithione (2), an assumed zwitterion undergoes ring expansion. In analogous reactions, unstrained thiones afford thiiranes, possibly by ring closure of the postulated intermediates or by concerted addition. Desulfurization of thiiranes, which occurs spontaneously in some instances, results in the formation of ketene acetals, many of which hydrolyze during workup. O-Alkyl thioesters and xanthates react to afford products via insertion of the DMC into Csp2-O or Csp2-S bonds, respectively. Copyright
Reactions of dimethoxycarbene with thiocarbonyl compounds
Dawid, Malgorzata,Mloston, Grzegorz,Reid, Darren L.,Warkentin, John
, p. 1025 - 1028 (2003)
A diverse sample of thiocarbonyl compounds were examined to determine what the ultimate stable products are of their reactions with dimethoxycarbene. Those ultimate products can be significantly different for an oxyphosphinyl dithioformate, methyl dithiobenzoate, O-methyl thiobenzoate, and dimethyl xanthate.
Preparation method of penta-deuterium atom substituted 2-thiophenobarbital
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Paragraph 0021-0022, (2021/07/08)
The invention discloses a preparation method of penta-deuterium atom substituted 2-thiophenobarbital, and belongs to the field of organic synthesis and analysis detection. The preparation method comprises the steps that the penta-deuterium atom substituted 2-thiophenobarbital is prepared from methyl malonate as a raw material through Friedel-Crafts alkylation reaction, cyclization reaction and nucleophilic substitution reaction, separation and purification. The prepared deuterated 2-thiophenobarbital has the advantages of high chemical purity, stable deuterium atoms and the like. The method disclosed by the invention is simple to operate, high in yield and low in cost. The invention not only provides a synthesis method of penta-deuterium atom substituted 2-thiophenobarbital with independent intellectual property rights, but also provides a deuterated internal standard substance for analysis and detection.
A concise route towards isoflavans
Basuli, Suchand,Chinnabattigalla, Sreenivasulu,Gupta, Kshitija,Gedu, Satyanarayana
, p. 182 - 194 (2020/10/19)
Isoflavans have gained considerable interest owing to their potential health benefits. Herein, we have presented a straightforward strategy for isoflavans synthesis. The strategy features an intermolecular [Cu]-catalyzed arylation of malonates and an intr
Radical Addition Enables 1,2-Aryl Migration from a Vinyl-Substituted All-Carbon Quaternary Center
Li, Zexian,Shi, Zhuangzhi,Wang, Minyan
supporting information, p. 186 - 190 (2020/11/02)
An efficient method for photocatalytic perfluoroalkylation of vinyl-substituted all-carbon quaternary centers involving 1,2-aryl migration has been developed. The rearrangement reactions use fac-Ir(ppy)3, visible light and commercially available fluoroalkyl halides and can generate valuable multisubstituted perfluoroalkylated compounds in a single step that would be challenging to prepare by other methods. Mechanistically, the photoinduced alkyl radical addition to an alkene leads to the migration of a vicinal aryl substituent from its adjacent all-carbon quaternary center with the concomitant generation of a C-radical bearing two electron-withdrawing groups that is further reduced by a hydrogen donor to complete the domino sequence.
F--Free Deoxyhydrotrifluoromethylation of α-Keto Esters with Ph3P+CF2CO2-: Synthesis of α-CF3-Substituted Esters
Jia, Yimin,Jiang, Zhong-Xing,Yang, Zhigang,Yuan, Yuan,Zheng, Ying
, p. 10913 - 10923 (2020/09/23)
Trifluoromethylated compounds are usually obtained via trifluoromethylation reaction by the use of CF3SiMe3 and NaSO2CF3, Umemoto's and Togni's reagents. Here, an external fluorine anion-free direct deoxyhydrotrifluoromethylation of α-keto esters with a d
UV-mediated decomposition of diazomalonates in benzene: Unexpected access to functionalized bicyclo[3.2.0]heptane skeleton
Chiang, Yi-Jung,Zhu, Jia-Liang
supporting information, p. 3081 - 3084 (2017/07/17)
Upon irradiation with 300-nm UV light, the photolysis of diazomalonates in benzene unexpectedly affords 2,6-dicarboxylate bicyclo[3.2.0]hepta-2,6-dienes in low yields. These products are proven to be derived from cyclohepta-1,3,5-triene intermediates presumably via a tandem 1,5-carboxylate migration/[2+2] cycloaddition sequence.
Protonation and transformations of α-diazo-β-dicarbonyl compounds in superacids: generation of the strongest carbon-centered cationic electrophiles at the protonation of diazomalonates in Friedel–Crafts reactions
Satumov, Eugeniy T.,Medvedev, Jury J.,Nilov, Denis I.,Sandzhieva, Maria A.,Boyarskaya, Irina A.,Nikolaev, Valerij A.,Vasilyev, Aleksander V.
, p. 4835 - 4844 (2016/07/18)
Protonation of diazodiketones N2C(COR)2in Br?nsted superacids (TfOH, FSO3H, TfOH–SbF5) gives rise to stable and non-reactive O,O-diprotonated at carbonyl oxygens species N2C(C(=OH+)R)2, which were studied by means of1H and13C NMR. Diazomalonates N2C(CO2Alk)2, contrary to diazodiketones, react with TfOH or HF, releasing nitrogen and producing triflates of oxymalonates TfOCH(CO2Alk)2or fluoromalonates FCH(CO2Alk)2, respectively. Diazoketoesters N2C(COR)(CO2Alk) react in the same way only with TfOH, but not with HF. The reactions of diazomalonates with arenes ArH (benzene, toluene, xylenes) in TfOH solution yield corresponding Friedel–Crafts reaction products ArCH(CO2Alk)2. According to performed DFT calculations, trication+CH(C(=OH+)OMe)2, a possible intermediate, which is derived from protonation of dimethyl diazomalonate, should be the strongest cationic carbon-centered electrophile known up to date.
Gold(I)-Catalyzed Enantioselective Desymmetrization of 1,3-Diols through Intramolecular Hydroalkoxylation of Allenes
Zi, Weiwei,Toste, F. Dean
supporting information, p. 14447 - 14451 (2016/01/25)
A gold(I)-catalyzed enantioselective desymmetrization of 1,3-diols was achieved by intramolecular hydroalkoxylation of allenes. The catalyst system 3-F-dppe(AuCl)2 /(R)-C8-TRIPAg proved to be specifically efficient to promote the desymmetrizing cyclization of 2-aryl-1,3-diols, which have proven challenging substrates in previous reports. Multisubstituted tetrahydrofurans were prepared in good yield with good enantioselectivity and diastereoselectivity by this method.
-Catalyzed cascade arylation and chlorination of α-diazocarbonyl compounds with arylboronic acids and n -chlorosuccinimide for facile synthesis of α-aryl-α-chloro carbonyl compounds
Ng, Fo-Ning,Lau, Yan-Fung,Zhou, Zhongyuan,Yu, Wing-Yiu
supporting information, p. 1676 - 1679 (2015/04/14)
A Rh(III)-catalyzed cascade arylation and chlorination of α-diazocarbonyl compounds with arylboronic acids and N-chlorosuccinimide was achieved. The reaction exhibits excellent functional group tolerance on the organoboron and the diazo reagents; the functionalized α-aryl-α-chlorocarbonyl compounds were obtained in up to 86% yields. The cascade reaction should involve migratory carbene insertion of arylrhodium(III) to form some reactive rhodium(III)-diketonate complexes. Its subsequent reaction with N-chlorosuccinmide afforded the α-chlorocarbonyl products.
