A theoretical study of face selectivity in the michael addition of a grignard reagent with 5-substituted-2-dicyanomethyleneadamantanes

Pei Fang Wu, I. Ting Wang, Hsiu Feng Lu, Ching Fa Yao, Ying Chieh Sun

Research output: Contribution to journalArticle

Abstract

Face selectivity for the reactions of 5-substituted (X)-2- dicyanomethyleneadamantanes with a Grignard reagent was examined using ab initio calculation for the substituents (X=F, Cl, Br, OH, NH2, and CH 3). The calculated syn/anti product ratio based, on the results of transition state energies for the halide substituents are in good agreement with the available experimental results. In addition, the results of the natural bond orbital calculation suggest that the through-bond Cieplak hyperconjugation effect, instead of the through-space interaction suggested by the experimental results in a prior study, is the main factor in determining face selectivity for the halide substituents in the present study, while for (X=OH, NH2, and CH3) substituents, other interactions may have unnegligible effects as well.

Original languageEnglish
Pages (from-to)545-549
Number of pages5
JournalJournal of the Chinese Chemical Society
Volume50
Issue number3 B
DOIs
Publication statusPublished - 2003 Jan 1

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Orbital calculations
Electron transitions
Electron energy levels

Keywords

  • Adamantane
  • Face selectivity
  • Nucleophilic addition
  • Quantum chemistry calculation

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

A theoretical study of face selectivity in the michael addition of a grignard reagent with 5-substituted-2-dicyanomethyleneadamantanes. / Wu, Pei Fang; Wang, I. Ting; Lu, Hsiu Feng; Yao, Ching Fa; Sun, Ying Chieh.

In: Journal of the Chinese Chemical Society, Vol. 50, No. 3 B, 01.01.2003, p. 545-549.

Research output: Contribution to journalArticle

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abstract = "Face selectivity for the reactions of 5-substituted (X)-2- dicyanomethyleneadamantanes with a Grignard reagent was examined using ab initio calculation for the substituents (X=F, Cl, Br, OH, NH2, and CH 3). The calculated syn/anti product ratio based, on the results of transition state energies for the halide substituents are in good agreement with the available experimental results. In addition, the results of the natural bond orbital calculation suggest that the through-bond Cieplak hyperconjugation effect, instead of the through-space interaction suggested by the experimental results in a prior study, is the main factor in determining face selectivity for the halide substituents in the present study, while for (X=OH, NH2, and CH3) substituents, other interactions may have unnegligible effects as well.",
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AU - Wu, Pei Fang

AU - Wang, I. Ting

AU - Lu, Hsiu Feng

AU - Yao, Ching Fa

AU - Sun, Ying Chieh

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N2 - Face selectivity for the reactions of 5-substituted (X)-2- dicyanomethyleneadamantanes with a Grignard reagent was examined using ab initio calculation for the substituents (X=F, Cl, Br, OH, NH2, and CH 3). The calculated syn/anti product ratio based, on the results of transition state energies for the halide substituents are in good agreement with the available experimental results. In addition, the results of the natural bond orbital calculation suggest that the through-bond Cieplak hyperconjugation effect, instead of the through-space interaction suggested by the experimental results in a prior study, is the main factor in determining face selectivity for the halide substituents in the present study, while for (X=OH, NH2, and CH3) substituents, other interactions may have unnegligible effects as well.

AB - Face selectivity for the reactions of 5-substituted (X)-2- dicyanomethyleneadamantanes with a Grignard reagent was examined using ab initio calculation for the substituents (X=F, Cl, Br, OH, NH2, and CH 3). The calculated syn/anti product ratio based, on the results of transition state energies for the halide substituents are in good agreement with the available experimental results. In addition, the results of the natural bond orbital calculation suggest that the through-bond Cieplak hyperconjugation effect, instead of the through-space interaction suggested by the experimental results in a prior study, is the main factor in determining face selectivity for the halide substituents in the present study, while for (X=OH, NH2, and CH3) substituents, other interactions may have unnegligible effects as well.

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