<電子ブック>
Substituent Effects in Radical Chemistry

責任表示
著者
本文言語
出版者
出版年
出版地
関連情報
概要 Respectably old radical chemistry which plays a rna jor role in life-processes, both desired (breathing, ... ) and non-desired (in flammatory diseases, ageing, ... ) has been gaining new youth in the ...past decade. Modern spectroscopy and other physical methods, recent advances in computational methods as well as impressive and mechanistically well-understood syntheses have led to a number of spectacular deve lopments in the field of radical chemistry. The impact of these achi evements will reach far beyond the field of organic chemistry, for example into biology and medicine. New facts and concepts in this rapidly expanding field deserved discussion among a number of leading experts present at the Workshop both for the information and constructive criticism. This happened during a particular brainstorming session and some of the impressions and reflections exchanged are recorded in the Epilogue. Indeed the topic chosen seems to be quintessential for the whole radical chemistry understanding and exploiting (single and multiple) substituent effects on radicals. We had the honour to organise this Workshop because some years ago, in collaboration with L. Stella, we became involved in radical stabi lising effects when both a donor and an acceptor (captor) groups are present on a C-radical. This leads to an enhanced stabilisation which we called the captodative effect and we have endeavoured the first extensi ve investigation of this effect on carbon centered radicals.続きを見る
目次 1. A Theoretical Approach to Substituent Effects in radical Chemistry
2. Sigma and Pi Effects in Radicals
3. The Contrasting Strain Energies of Small Ring Carbon and Silicon Rings. The Relationship with Free Radical Energies
4. Allylic and Allenic Capto-dative Stabilization in Nitrogen Centered Free Radicals
5. Conformational Preferences in Beta Substituted Ethyl Radicals A Quantitative Analysis of Hyperconjugation, Homoconjugation, d-Orbital and Steric Effects
6. Substituent Effects on the Thermochemistry and Electrochemistry of Free Radicals
7. Some Applications of ES? Spectroscopy to the Study of Substituent Effects
8. Substituent Effects on Absolute Rate Constants and Arrhenius Parameters for the Addition of tert-Butyl Radicals to Alkenes
9. Allylic Radicals-An ESR Spectroscopical Study
10. ESR-Spectroscopical Investigation of Capto-dative Substituent Effects in Benzyl Radicals
11. The Effect of Substituents on Benzylic Radical ESR Hyperfine Coupling Constants. The ?? Scale Based Upon Spin Delocalization
12. Determination of Thermodynamic Stabilisation in Amino-Substituted Alkyl radicals
13. Phosphinylhydrazyls R2 NNP(O)L2. Influence of the Phosphinyl Group on the 3-Electron NN Pi Bond
14. Substituent Effects on the Dimerization of Vinyl Nitroxides and on the Dissociation of Their Tricyclic Dimers
15. Substituent Effects on the CC-Bond Strength
16. The Different Recombinations of Diphenyl Methyl Radicals Ph2 C°-R, R = tBu, CN, COOR', COR'
17. Some Chemistry of Radical Ions
18. Substituent Effects on the Methylenecyclopropane Rearrangement. A Probe for Free Radical Effects
19. 2-Oxomorpholin-3-yl Radicals
20. Azoalkane Decompositions as Measures of Radical Substituent Effects
21. Orbital Effects in Carbohydrate Radicals
22. ESR-Spectroscopical Investigation of Carbohydrate Radicals in Solution. Radical Stabilization by Beta C-0 Bonds
23. Studies on the Captodative' Effect. Entropy/Enthalpy Compensation as Solvent Effect in Radical Forming Reactions. A relative Radical Stabilisation Scale
24. ?° Revisited
25. Captodative Effect on the relative Rates of H-Abstraction by Tert-Butoxy Radicals
26. Substituent Effects in Gas-Phase Thermal Hydroxylation and Hydrogenolysis
27. Heterocyclic Substituents in SRNl Reactions
28. Substituent Effects on the Oxidation of Toluenes by Molecular Oxygen: The Surprising Reactivity of p-Methoxytoluene
29. Free Radical Additions of Dichloromethahe to ?-Alkenyl t-Butyl Peroxides
30. The Non-Chain Radicaloid Mechanism of Some Nucleophilic Substitution Reactions
31. Captodative Substituent Effects in Cycloaddition Reactions
32. Captodative Substitution Effect in [2+2] Cycloadditions Between Alienes and Olefins
33. Captodative Alkenes as Dipolarophiles-Kinetic Studies
34. Captodative Alkenes in Concerted 1, 3-Dipolar Cycloadditions
35. Photo-Diels-Alder Addition of Two Captodative Alkenes to 1-Acetonaphtone
36. Free Radical Cyclization of Unsaturated Carbonic acid Derivatives
37. Synthetic Applications of the Polar Effects of the Substituents in Free-Radical Reactions
38. Selectivity in Homolytic Aromatic Substitutions. Alkylations of Pyridines
39. The Invention of High-Yielding Radical Chain Reactions
40. Epilogue
Participants.
続きを見る
本文を見る Full text available from SpringerLink ebooks - Physics and Astronomy (Archive)

詳細

レコードID
主題
SSID
eISBN
登録日 2020.06.27
更新日 2020.06.28