期刊
CHEMISTRYSELECT
卷 8, 期 39, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/slct.202302205
关键词
nitroacrylates; cations; oximes; triflic acid; atropoisomers
Methyl or ethyl 3-nitropropenoates react with arenes in triflic acid tetrahydrofuran solution to form oximes of alkyl 2,3-diaryl-3-oxopropanoates in good yields. The obtained oximes exhibit atropoisomerism due to the presence of ortho-methyl substituents in the aryl ring. The reactive electrophiles in this reaction are AlkO(HO+)C1-C2H=C3H-N+(O)(OH) species protosolvated on the NO2 and CO2R acceptor groups.
Methyl or ethyl 3-nitropropenoates (beta-nitroacrylates) AlkO(O)C1-C2H=C3H-NO2 in reaction with arenes ArH in triflic acid CF3SO3H (TfOH) at room temperature in 1 h give rise to oximes of alkyl 2,3-diaryl-3-oxopropanoates AlkO(O)C-CH(Ar)-C(Ar)=NOH in yields of 42-92 %. The obtained oximes bearing ortho-methyl substituents in the aryl ring exist as atropoisomers in solutions. The study of protonated forms of beta-nitroacrylates by NMR and DFT calculations has revealed that the reactive electrophiles are species AlkO(HO+)C1-C2H=C3H-N+(O)(OH) protosolvated on the acceptor groups NO2 and CO2R. Plausible reaction mechanism is based on the primary interaction of aromatic nucleophiles with these electrophilic species onto their carbon C2.
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