Cyclopropylcarbinyl-Type Ring Openings. Reconciling the Chemistry of Neutral Radicals and Radical Anions
- 28 March 2002
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 124 (16) , 4271-4281
- https://doi.org/10.1021/ja0041831
Abstract
Cyclopropylcarbinyl → homoallyl and related rearrangements of radical ions (a) are frequently used as mechanistic “probes” to detect the occurrence of single electron transfer in chemical and biochemical processes, (b) provide the basis for mechanism-based drug design, and (c) are important tools in organic synthesis. Unfortunately, these rearrangements are poorly understood, especially with respect to the effect of substrate structure on reactivity. Frequently, researchers assume that the same factors which govern the reactivity of neutral free radicals also pertain to radical ions. The results reported herein demonstrate that in some cases structure−reactivity trends in radical ion rearrangements are very different from neutral radicals. For radical ions, delocalizations of both charge and spin are important factors governing their reactivity.Keywords
This publication has 40 references indexed in Scilit:
- The Vinylcyclopropane Radical Cation Rearrangement and Related Reactions on the C5H8•+HypersurfaceJournal of the American Chemical Society, 1999
- Kinetics of the Reduction of Dialkyl Peroxides. New Insights into the Dynamics of Dissociative Electron Transfer1Journal of the American Chemical Society, 1999
- Nature of Methyl and Silyl Mesolytic Dissociations in Substituted Cyclopropenyl Radical Cations and Anions. A CAS-MCSCF and CCSD(T) Theoretical StudyThe Journal of Organic Chemistry, 1999
- Radical Ion Probes. 8. Direct and Indirect Electrochemistry of 5,7-Di-tert-butylspiro[2.5]octa-4,7-dien-6-one and DerivativesJournal of the American Chemical Society, 1998
- Electron-Transfer Reactions of Aromatic α,β-Epoxy Ketones: Factors That Govern Selective Conversion to β-Diketones and β-Hydroxy KetonesThe Journal of Organic Chemistry, 1997
- Radical ion probes. 2. Evidence for the reversible ring opening of arylcyclopropylketyl anions. Implications for mechanistic studiesJournal of the American Chemical Society, 1992
- Reversible cyclopropyl ring opening of 1-aroyl-2-phenylcyclopropane radical anions. Determination of the ring opening and closure rates of the intermediate ketylsJournal of the American Chemical Society, 1992
- Structure of Meerwein's ester and of its benzene inclusion compoundJournal of the American Chemical Society, 1984
- Reaction of dimethylsulfoxonium methylide and griseofulvinThe Journal of Organic Chemistry, 1971
- Synthesis of N-Benzoyl-2'-O-tetrahydropyranylguanosine-5'-phosphate, an Intermediate in the Chemical Synthesis of Polyriboguanylic Acid1Journal of the American Chemical Society, 1965