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Updated: Aug 27, 2026

Metal-free Synthesis of Ynones from Acyl Chlorides and Potassium Alkynyltrifluoroborate Salts
Published on: February 24, 2015
Solvation effects on alternative nucleophilic substitution reaction paths for chloride/allyl chloride and
Bethany L Kormos1, Christopher J Cramer
1Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant St SE, Minneapolis, Minnesota 55455-0431, USA.
Abstract:
An adiabatic connection method, mPW1PW91(0.581)/6-31G(d), was employed in conjunction with the continuum solvation model SM5.42 to study the effects of solvation on the S(N)1, S(N)2, and syn and anti S(N)2' nucleophilic substitution reactions of chloride anion with allyl chloride and its gamma-methylated analogues Z- and E-crotyl chloride and isoprenyl chloride. The impact of equilibrium solvation on the potential energy surfaces of these systems is large and leads to significant changes in both the geometries and the relative energetics of different reaction pathways for different species. The predicted effects of increased solvent dielectric constant are consistent with available experimental data and provide semiquantitative insights into the relative influence of different solvents on particular properties.
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