Polarity, regioselectivity, and reactivity of free radicals in reactions involving addition to olefins

Journal Article · Wed Dec 10 00:00:00 EST 1986 · J. Org. Chem. USSR (Engl. Transl.); (United States)

OSTI ID:6388598

Volovik, S V; Dyadyusha, G G; Staninets, V I

A conception of the polarity (philicity) of free radicals and a charge-transfer model based on it and the stabilization-energy method for the regioselectivity and reactivity of radicals in addition processes have been developed in the framework of one-electron perturbation theory. The key aspects of the variation of the regiochemistry and reactivity with the electronic structure of the free radical and the substrate have been discussed. The predominant direction of an addition process and the relative reactivity are controlled by electronic effects and can be predicted on the basis of an analysis of the frontier orbitals of the interactions in the free-radical-substrate system. The effectiveness of the approach has been illustrated in examples of reactions involving the addition of alkyl and heterocyclic radicals to olefins with various types of substituents. Other applications of the model (intermolecular addition at a double bond (the cyclization of radicals) and radical copolymerization) and prospects for further application have been discussed briefly.

• Research Organization: Institute of Organic Chemistry, Kiev, USSR
• OSTI ID: 6388598
• Journal Information: J. Org. Chem. USSR (Engl. Transl.); (United States), Vol. 22:7; Other Information: Translated from Zh. Org. Khim.; 22: No. 7, 1359-1374(Jul 1986)
• Country of Publication: United States
• Language: Russian

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS
RADICALS
ACTIVATION ENERGY
ATOMIC MODELS
ELECTRON TRANSFER
ELECTRONIC STRUCTURE
MOLECULAR MODELS
SPIN ORIENTATION
AFFINITY
ALKENES
ALKYL RADICALS
ARRHENIUS EQUATION
BINDING ENERGY
CHARGE DISTRIBUTION
CHEMICAL BONDS
CHEMICAL REACTION KINETICS
CONFIGURATION INTERACTION
COPOLYMERIZATION
DEHYDROCYCLIZATION
ENERGY GAP
FLUORINATED ALIPHATIC HYDROCARBONS
HETEROCYCLIC COMPOUNDS
IONIZATION POTENTIAL
MOLECULAR ORBITAL METHOD
MOLECULAR STRUCTURE
PERTURBATION THEORY
POLYATOMIC MOLECULES
QUANTUM MECHANICS
STEREOCHEMISTRY
VALENCE
CHEMICAL REACTIONS
ENERGY
EQUATIONS
HALOGENATED ALIPHATIC HYDROCARBONS
HYDROCARBONS
KINETICS
MATHEMATICAL MODELS
MECHANICS
MOLECULES
ORGANIC COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORIENTATION
POLYMERIZATION
REACTION KINETICS
400201* - Chemical & Physicochemical Properties
640302 - Atomic
Molecular & Chemical Physics- Atomic & Molecular Properties & Theory