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Electrophilic Addition to Alkenes: The Relation between Reactivity and Enthalpy of Hydrogenation: Regioselectivity is Determined by the Stability of the Two Conceivable Products
Author(s) -
Schnatter Wayne F. K.,
Rogers Donald W.,
Zavitsas Andreas A.
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201500314
Subject(s) - alkene , regioselectivity , chemistry , electrophile , carbocation , electrophilic addition , heteroatom , allylic rearrangement , free radical addition , organic chemistry , reactivity (psychology) , carbene , free energy relationship , computational chemistry , medicinal chemistry , ring (chemistry) , reaction rate constant , catalysis , kinetics , medicine , alternative medicine , pathology , physics , quantum mechanics
Although electrophilic addition to alkenes has been well studied, some secrets still remain. Halogenations, hydrohalogenations, halohydrin formations, hydrations, epoxidations, other oxidations, carbene additions, and ozonolyses are investigated to elucidate the relation of alkene reactivities with their enthalpies of hydrogenation (Δ H hyd ). For addition of electrophiles to unconjugated hydrocarbon alkenes, ln( k ) is a linear function of Δ H hyd , where k is the rate constant. Linear correlation coefficients are about 0.98 or greater. None of the many previously proposed correlations of ln( k ) with the properties of alkenes or with linear free‐energy relationships match the generality and accuracy of the simple linear relationship found herein. A notable exception is acid‐catalyzed hydration in water or in solvents stabilizing relatively stable carbocation intermediates (e.g., tertiary, benzylic, or allylic). 13 C NMR chemical shifts of the two alkene carbons also predict regioselectivity. These effects have not been noted previously and are operative in general, including addition to heteroatom‐substituted alkenes.