The impact of substituents on the transition states of SN2 and E2 reactions in aliphatic and vinylic systems: remarkably facile vinylic eliminations

Journal of the American Chemical Society
Samuel NetteyS Gronert

Abstract

For a series of α and β substituted haloethanes and haloethenes, gas-phase experiments and computational modeling have been used to characterize their nucleophilic substitution and elimination reactions. Despite being less thermodynamically favorable, the vinylic eliminations have rate constants and computed barriers that are similar to those of analogous aliphatic eliminations. This is the result of the vinylic systems shifting to more E1(cb)-like transition states and exploiting the inherent greater acidity of vinylic hydrogens. In general, the α-substituents have a greater impact on the S(N)2 pathways and stabilize the transition states via field and polarizability effects. Substantial stabilization is also provided to the E2 transition states by the α-substituents, but they have surprisingly little impact on the geometries of the transition states of either pathway. The β-substituents generally lead to a strong bias toward elimination and greatly affect the synchronicity of the elimination (more E1(cb)-like) as well as its location on the reaction coordinate (early). The experimental and computational data are in good accord, and the full data set provides a comprehensive picture of substituent effects on solvent-free S(N)2...Continue Reading

References

Nov 20, 2001·Chemical Reviews·S Gronert
Mar 23, 2002·Science·Colleen K ReganJohn I Brauman
Sep 25, 2004·Mass Spectrometry Reviews·Scott Gronert
Oct 8, 2004·Journal of the American Chemical Society·Scott GronertLawrence M Pratt

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Citations

Oct 19, 2013·Journal of the American Society for Mass Spectrometry·Allison D EanesScott Gronert
Nov 18, 2018·Journal of Mass Spectrometry : JMS·Tobias Parchomyk, Konrad Koszinowski
Apr 14, 2015·Angewandte Chemie·Christopher A Swift, Scott Gronert
May 4, 2017·Annual Review of Physical Chemistry·Jennifer Meyer, Roland Wester
Mar 26, 2019·The Journal of Organic Chemistry·Leah L Donham, Scott Gronert
Jan 18, 2013·Journal of the American Chemical Society·Jochen MikoschRoland Wester
Jan 21, 2014·The Journal of Organic Chemistry·Paul R RablenJean E Schneider
Jul 31, 2013·The Journal of Organic Chemistry·Keyanna M Conner, Scott Gronert
Jan 31, 2015·Organic Letters·Francisco MéndezJulio A Alonso

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