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A Theoretical Study of Face Selectivity in the Michael Addition of a Grignard Reagent with 5‐Substituted‐2‐dicyanomethyleneadamantanes
Author(s) -
Wu PeiFang,
Wang ITing,
Lu HsiuFeng,
Yao ChingFa,
Sun YingChieh
Publication year - 2003
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.200300080
Subject(s) - chemistry , hyperconjugation , selectivity , reagent , halide , ab initio , computational chemistry , medicinal chemistry , organic chemistry , molecule , catalysis
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, NH 2 , 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, NH 2 , and CH 3 ) substituents, other interactions may have unnegligible effects as well.