Computations Reveal That Electron-Withdrawing Leaving Groups Facilitate Intramolecular Conjugate Displacement Reactions by Negative Hyperconjugation

2016 ◽  
Vol 81 (10) ◽  
pp. 4290-4294 ◽  
Author(s):  
Elizabeth L. Noey ◽  
Gonzalo Jiménez-Osés ◽  
Derrick J. L. Clive ◽  
K. N. Houk
Keyword(s):  
Displacement Reactions ◽  
Negative Hyperconjugation ◽  
Intramolecular Conjugate Displacement ◽  
Leaving Groups

Impact of Electronic Effects on the Nucleofugality of Leaving Groups

Synthesis ◽  
2017 ◽  
Vol 49 (15) ◽  
pp. 3422-3432 ◽  
Author(s):  
Bernard Denegri ◽  
Mirela Matić ◽  
Olga Kronja
Keyword(s):  
Short Review ◽  
Linear Free Energy Relationship ◽  
Electronic Effects ◽  
Resonance Effects ◽  
Linear Free Energy ◽  
Leaving Group ◽  
Negative Hyperconjugation ◽  
Leaving Groups ◽  
The Impact ◽  
Leaving Group Ability

A short review of the development of nucleofugality and electrofugality scales based on solvolysis rates of benzhydryl derivatives is presented. Accordingly, the rate of the heterolytic step in the SN1 displacement reaction and the leaving group ability (nucleofugality) in a given solvent are related with the special linear free-energy relationship (LFER) equation: log k = s f (N f + E f). The impact of electronic effects in the leaving group (nucleofuge) on the overall SN1 reactivity of the substrate is given. The importance of inductivity, resonance, polarity and field effects in the leaving group moiety in the transition state is analyzed. Also, the effect of the negative hyperconjugation and the influence of other electronic effects in the leaving group on the height of the reaction intrinsic barrier are considered.1 Introduction2 Development of the Nucleofugality Scale3 Inductive and Resonance Effects4 Negative Hyperconjugation5 Intrinsic Barrier6 Conclusions

Diazeniumdiolate Ions as Leaving Groups in Anomeric Displacement Reactions:  A Protection−Deprotection Strategy for Ionic Diazeniumdiolates

2005 ◽  
Vol 127 (41) ◽  
pp. 14188-14189 ◽  
Author(s):  
Brett M. Showalter ◽  
Melissa M. Reynolds ◽  
Carlos A. Valdez ◽  
Joseph E. Saavedra ◽  
Keith M. Davies ◽  
...  
Keyword(s):  
Displacement Reactions ◽  
Leaving Groups
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