Homolytic Substitution Reaction at a Silicon Atom

1992 ◽  
Vol 75 (3) ◽  
pp. 935-939 ◽  
Author(s):  
Klaus. Kulicke ◽  
Chryss Stomos Chatgilialoglu ◽  
Birgit Kopping ◽  
Bernd Iese
Keyword(s):  
Silicon Atom ◽  
Substitution Reaction ◽  
Homolytic Substitution

Electron transference in hemolytic aromatic substitution reactions

1970 ◽  
Vol 48 (6) ◽  
pp. 1019-1020 ◽  
Author(s):  
Dennis D. Davis ◽  
Fauzia Y. Ahmed
Keyword(s):  
Charge Transfer ◽  
Complex Formation ◽  
Transition State ◽  
Substitution Reaction ◽  
Methyl Radicals ◽  
Aromatic Substitution ◽  
Substitution Reactions ◽  
A Charge ◽  
Homolytic Substitution

The selectivity of methyl radicals in the homolytic substitution reaction on naphthalene was studied as a function of solvent. The selectivity decreases as the solvent dielectric increases. A possible explanation of these effects based upon a charge-transfer contribution to the transition state leading to σ-complex formation is offered.

Réactions de substitution homolytique. V. Stéréosélectivité de différents radicaux cyclohexyles

1976 ◽  
Vol 54 (6) ◽  
pp. 905-909 ◽  
Author(s):  
Michel Gruselle ◽  
Jacques Fossey ◽  
Daniel Lefort ◽  
Claude Lamarre ◽  
Jean-Claude Richer
Keyword(s):  
Steric Hindrance ◽  
Substitution Reaction ◽  
Steric Effects ◽  
Relative Importance ◽  
Peroxy Acid ◽  
Radical Site ◽  
Peroxy Acids ◽  
Homolytic Substitution ◽  
Thermal Decarboxylation ◽  
As If

The influence of the environment near the radical site on the stereoselectivity of the homolytic substitution reaction of variously substituted cyclohexyl radicals on the peroxidic oxygen of a peroxy acid has been studied using the thermal decarboxylation of peroxy acids. This reaction leads to stereoisomeric alcohols[Formula: see text]The radical behaves as if it were planar and, in general, an axial approach of the reagent is strongly favoured except when substituents increase the steric hindrance of the radical.The stereoselectivity is explained in terms of the relative importance of steric effects (for the axial approach) and of bond interactions (for the equatorial approach). It also depends on the flexibility of the ring. [Journal translation]

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