103040-42-2Relevant articles and documents
Iodoarene-Catalyzed Oxyamination of Unactivated Alkenes to Synthesize 5-Imino-2-Tetrahydrofuranyl Methanamine Derivatives
Deng, Xiao-Jun,Liu, Hui-Xia,Zhang, Lu-Wen,Zhang, Guan-Yu,Yu, Zhi-Xiang,He, Wei
, p. 235 - 253 (2021/01/09)
Reported here is the room-temperature metal-free iodoarene-catalyzed oxyamination of unactivated alkenes. In this process, the alkenes are difunctionalized by the oxygen atom of the amide group and the nitrogen in an exogenous HNTs2 molecule. This mild and open-air reaction provided an efficient synthesis to N-bistosyl-substituted 5-imino-2-tetrahydrofuranyl methanamine derivatives, which are important motifs in drug development and biological studies. Mechanistic study based on experiments and density functional theory calculations showed that this transformation proceeds via activation of the substrate alkene by an in situ generated cationic iodonium(III) intermediate, which is subsequently attacked by an oxygen atom (instead of nitrogen) of amides to form a five-membered ring intermediate. Finally, this intermediate undergoes an SN2 reaction by NTs2 as the nucleophile to give the oxygen and nitrogen difunctionalized 5-imino-2-tetrahydrofuranyl methanamine product. An asymmetric variant of the present alkene oxyamination using chiral iodoarenes as catalysts also gave promising results for some of the substrates.
Harnessing Applied Potential: Selective β-Hydrocarboxylation of Substituted Olefins
Alkayal, Anas,Buckley, Benjamin R.,Malkov, Andrei V.,Montanaro, Stephanie,Tabas, Volodymyr,Wright, Iain A.
supporting information, (2020/02/13)
The construction of carboxylic acid compounds in a selective fashion from low value materials such as alkenes remains a long-standing challenge to synthetic chemists. In particular, β-addition to styrenes is underdeveloped. Herein we report a new electrosynthetic approach to the selective hydrocarboxylation of alkenes that overcomes the limitations of current transition metal and photochemical approaches. The reported method allows unprecedented direct access to carboxylic acids derived from β,β-trisubstituted alkenes, in a highly regioselective manner.
Facile synthesis of 2-aryl or β,γ-unsaturated esters via 1,2-Migration from aryl or α,β-unsaturated ketones using thallium(III) p-tosylate
Lee, Jae In
, p. 125 - 128 (2017/06/07)
The experiment reports that 2-aryl esters can be efficiently synthesized via 1,2-aryl migration from aryl ketones using thallium(III) p-tosylate in high yields. To determine optimum conditions for conversion of aryl ketones to 2-aryl esters, the effects of solvents were examined. An initial reaction of 4'-methoxypropiophenone and perchloric acid using thallium(III) p-tosylate in ethanol afforded ethyl 2-(4-methoxyphenyl)propanoate in only 10% yield after 24 h at room temperature. However, the corresponding reaction in ethanol/triethyl orthoformate (4/1) was completed in 1 h between 0 °C and room temperature to give ethyl 2-(4-methoxyphenyl)propanoate in 94% yield. The presence of triethyl orthoformate induced rapid ketalization of enol intermediate and facilitated 1,2-migration of the 4-methoxyphenyl group. The relative effectiveness of several metal salts was also examined for conversion of 2',4'-dimethoxypropiophenone to ethyl 2-(2,4-dimethoxyphenyl)propanoate. The solvents were evaporated off under reduced pressure, and the residue was dissolved in methylene chloride. The white precipitate was filtered off, and the resulting yellow solution was poured into saturated NaHCO3 solution and extracted with methylene chloride. The combined organic layers were dried over anhydrous MgSO4, filtered, and concentrated in vacuo. The residue was purified by vacuum distillation using a Kugelrohr apparatus to give 4g as a colorless liquid.
