Ab initio structures of transition states in electrophilic addition reactions of molecular halogens with ethene

1988 ◽  
pp. 532 ◽  
Author(s):  
Shinichi Yamabe ◽  
Tsutomu Minato ◽  
Satoshi Inagaki
Keyword(s):  
Ab Initio ◽  
Transition States ◽  
Electrophilic Addition ◽  
Addition Reactions

scholarly journals A Dynamic Picture of the Halolactonization Reaction through a Combination of ab-initio Metadynamics and Experimental Investigations .

2021 ◽  
Author(s):  
Ruben Van Lommel ◽  
Jonathan Bock ◽  
Constantin Daniliuc ◽  
Ulrich Hennecke ◽  
Frank De Proft
Keyword(s):  
Ab Initio ◽  
Electrophilic Addition ◽  
Experimental Investigations ◽  
Addition Reactions

The halolactonization reaction is one of the most common electrophilic addition reactions to alkenes. The mechanism is generally viewed as a two-step pathway, which involves the formation of an ionic...

[3,3] Sigmatropic Rearrangement of Some Fluorinated 1,5-Hexadienes

2002 ◽  
Vol 67 (10) ◽  
pp. 1517-1532 ◽  
Author(s):  
William R. Dolbier ◽  
Keith W. Palmer ◽  
Feng Tian ◽  
Piotr Fiedorow ◽  
Andrzej Zaganiaczyk ◽  
...  
Keyword(s):  
Experimental Data ◽  
Ab Initio ◽  
Transition States ◽  
Activation Parameters ◽  
Sigmatropic Rearrangement ◽  
Semiempirical Methods ◽  
Cope Rearrangement ◽  
Computational Studies ◽  
Stepwise Mechanism ◽  
Radical Intermediates

Fluorine atoms incorporated into 1,5-hexadiene molecule should influence the kinetic as well as the thermodynamic parameters of [3,3] sigmatropic rearrangement (Cope rearrangement). Within few decades is has been documented that this transformation proceeds in a concerted manner, rather than stepwise with some radical intermediates involved. Few new terminally fluorinated 1,5-hexadienes (compounds 3, 5A, 7, 9 and 5B) have been synthesized. The activation parameters of rearrangement have been determined and compared with those known for hydrocarbon analogues. While systems developing chair-like transition states (compounds 3 and 5) showed close similarity with hydrocarbon analogues (compound 1), those developing boat-like transition states (compounds 7, 9 and 5B) may proceed through radical stepwise mechanism. Computational studies of the transition states were carried out, showing that only ab initio methods (MP2 and especially DFT) can give approximate correlation with experimental data, whereas in the case of hydrocarbon analogues even simple semiempirical methods (AM1) were reliable enough to reproduce experimental results.

ELECTROPHILIC ADDITION REACTIONS OF FLUORO-OLEFINS

1966 ◽  
Vol 35 (6) ◽  
pp. 417-427 ◽  
Author(s):  
B L Dyatkin ◽  
E P Mochalina ◽  
Ivan L Knunyants
Keyword(s):  
Electrophilic Addition ◽  
Addition Reactions
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