Ab initio study of Lewis acid catalyzed nitrone cycloaddition to electron deficient alkenes. Does a Lewis acid catalyst change the reaction mechanism?

Junji Tanaka, Shuji Kanemasa

研究成果: ジャーナルへの寄稿記事

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Theoretical study of Lewis acid catalyzed nitrone cycloadditions to α,β-unsaturated carbonyl compounds is reported. Ab initio calculation using the 6-31++G** basis set has been applied to the model reaction between the parent nitrone (CH2=N(O)H) and acrolein (CH2=CHCHO) in the presence of BH3 or BF3 catalyst. Although the nitrone/BH3 complex is predominantly formed at the early stage of the reaction, the acrolein/BH3 complex as minor contributor shows high rate acceleration, giving the electronically controlled endo-isoxazolidine-4-carbaldehyde complex as the major regio- and stereoisomeric cycloadduct. On the other hand, the nitrone cycloaddition reaction of acrolein in the presence of BF3 leads to the formation of the corresponding Michael adduct complex intermediate which then cyclizes to the isoxazolidine-4-carbaldehyde complex. These calculation studies indicate that the nitrone cycloadditions with electron-deficient alkenes may proceed through a stepwise mechanism when catalyzed by a strong Lewis acid.

元の言語英語
ページ(範囲)899-905
ページ数7
ジャーナルTetrahedron
57
発行部数5
DOI
出版物ステータス出版済み - 1 28 2001

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

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