TY - JOUR
T1 - A theoretical study of face selectivity in the michael addition of a grignard reagent with 5-substituted-2-dicyanomethyleneadamantanes
AU - Wu, Pei Fang
AU - Wang, I. Ting
AU - Lu, Hsiu Feng
AU - Yao, Ching Fa
AU - Sun, Ying Chieh
PY - 2003
Y1 - 2003
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.
KW - Adamantane
KW - Face selectivity
KW - Nucleophilic addition
KW - Quantum chemistry calculation
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U2 - 10.1002/jccs.200300080
DO - 10.1002/jccs.200300080
M3 - Article
AN - SCOPUS:67249090046
SN - 0009-4536
VL - 50
SP - 545
EP - 549
JO - Journal of the Chinese Chemical Society
JF - Journal of the Chinese Chemical Society
IS - 3 B
ER -