Factors Controlling the Addition of Carbon‐Centered Radicals to Alkenes—An Experimental and Theoretical Perspective

TLDR

The field of radical C–C bond formation depends on known rate constants for carbon-centered radical addition to alkenes, and recent progress has provided many experimental constants and advanced quantum-chemical methods for accurate transition-state calculations. Herein we review this progress, recommend suitable experimental and theoretical procedures, and display representative data series for radical additions to alkenes. Guided by the state-correlation diagram for radical additions, we offer a new, more stringent quantification of the controlling factors. Our analysis revises previous qualitative rules, clarifies the interplay of enthalpy, polar charge-transfer, and steric effects, and introduces new non-linear predictive equations for rate constants that perform well in several tests but call for further theoretical and experimental foundation, with the same principles extending to polymer propagation, copolymerization, and radical additions to alkynes and aromatics.

Abstract

The successful exploitation of syntheses involving the generation of new carbon-carbon bonds by radical reactions rests on some prior knowledge of the rate constants for the addition of carbon-centered radicals to alkenes and other unsaturated molecules, and of the factors controlling them. Two former classical reviews in Angewandte Chemie by Tedder (1982) and by Giese (1983) provided mechanistic insight and led to various qualitative rules on the complex interplay of enthalpic, polar, and steric effects. In the meantime, the field has experienced very rapid progress: many more experimental absolute rate constants have become available, and there have been major advances in the efficiency and reliability of quantum-chemical methods for the accurate calculation of transition structures, reaction barriers, and reaction enthalpies. Herein we review this progress, recommend suitable experimental and theoretical procedures, and display representative data series for radical additions to alkenes. On this basis, and guided by the pictorial tool of the state-correlation diagram for radical additions, we then offer a new and more stringent quantification of the controlling factors. Our analysis leads to a partial revision of the previous qualitative rules, and it more clearly exhibits the interplay of the reaction enthalpy effects, polar charge-transfer contributions, and steric substituent effects on the reaction energy barrier. The various contributions are cast into the form of new, simple, and physically meaningful but non-linear, predictive equations for the preestimation of rate constants. These equations prove successful in several tests but call for additional theoretical and experimental foundation. The kinetics of related reactions such as polymer propagation, copolymerization, and the addition of radicals to alkynes and aromatic compounds is shown to follow the same principles.