LEADER 05548nam 2200721Ia 450 001 9910828353703321 005 20200520144314.0 010 $a1-282-49088-5 010 $a9786612490880 010 $a0-470-58411-4 010 $a0-470-58410-6 035 $a(CKB)2550000000007166 035 $a(EBL)484868 035 $a(OCoLC)521031694 035 $a(SSID)ssj0000335547 035 $a(PQKBManifestationID)11230182 035 $a(PQKBTitleCode)TC0000335547 035 $a(PQKBWorkID)10272548 035 $a(PQKB)10859431 035 $a(MiAaPQ)EBC484868 035 $a(Au-PeEL)EBL484868 035 $a(CaPaEBR)ebr10361290 035 $a(CaONFJC)MIL249088 035 $a(PPN)160471532 035 $a(EXLCZ)992550000000007166 100 $a20090814d2010 uy 0 101 0 $aeng 135 $aurcn||||||||| 181 $ctxt 182 $cc 183 $acr 200 00$aCarbon-centered free radicals and radical cations $estructure, reactivity, and dynamics /$fedited by Malcolm D. Forbes 205 $a1st ed. 210 $aHoboken, NJ $cWiely$dc2010 215 $a1 online resource (395 p.) 225 1 $aWiley Series of Reactive Intermediates in Chemistry and Biology ;$vv.2 300 $aIncludes index. 311 $a0-470-39009-3 327 $aCARBON-CENTERED FREE RADICALS AND RADICAL CATIONS; CONTENTS; About the Volume Editor; Preface to Series; Introduction; Contributors; 1. A Brief History of Carbon Radicals; 2. Intermolecular Radical Additions to Alkynes: Cascade-Type Radical Cyclizations; 2.1 Introduction; 2.2 Cascade Reactions Involving Radicals of Second Row Elements; 2.2.1 Cascade Reactions Initiated by Addition of C-Centered Radicals to Alkynes; 2.2.2 Cascade Reactions Initiated by Addition of O-Centered Radicals to Alkynes (Self-Terminating Radical Oxygenations) 327 $a2.2.3 Cascade Reactions Initiated by Addition of N-Centered Radicals to Alkynes 2.3 Cascade Reactions Initiated by Addition of Higher Main Group (VI)-Centered Radicals to Alkynes; 2.3.1 Cascade Reactions Initiated by Addition of Sn-Centered Radicals to Alkynes; 2.4 Cascade Reactions Initiated by Addition of Higher Main Group (VI)-Centered Radicals to Alkynes; 2.4.1 Cascade Reactions Initiated by Addition of S-Centered Radicals to Alkynes; 2.4.2 Cascade Reactions Initiated by Addition of Se-Centered Radicals to Alkynes 327 $a2.5 Cascade Reactions Initiated by Addition of Higher Main Group (V)-Centered Radicals to Alkynes 2.5.1 Cascade Reactions Initiated by Addition of P-Centered Radicals to Alkynes; 3. Radical Cation Fragmentation Reactions in Organic Synthesis; 3.1 Introduction; 3.1.1 Oxidative Carbon-Carbon Bond Cleavage; 3.1.2 Thermodynamic and Kinetic Considerations; 3.1.3 Reactive Intermediate Lifetime; 3.2 Electron Transfer-Initiated Cyclization Reactions; 3.2.1 Rate Enhancement and Mechanistic Studies; 3.2.2 Development of a Catalytic Aerobic Protocol; 3.2.3 Oxidative Cascade Reactions 327 $a3.3 Oxidative Acyliminium Ion Formation 3.4 Carbon-Carbon Bond Formation; 3.4.1 Chemoselectivity and Reactivity; 3.4.2 Reaction Scope; 3.5 Summary and Outlook; 4. Selectivity in Radical Cation Cycloadditions; 4.1 Introduction; 4.2 Mechanism and the Origin of the Rate Acceleration; 4.3 Selectivity in Radical Cation Cycloadditions; 4.4 Chemoselectivity; 4.4.1 Effect of Dienophile Substituents on Chemoselectivity; 4.4.2 Effect of Sensitizers and Solvents on Chemoselectivity; 4.4.3 Effect of Concentrations on Chemoselectivity; 4.4.4 Effect of Electron-Rich Dienophiles on Chemoselectivity 327 $a4.5 Regioselectivity 4.6 Periselectivity; 4.6.1 Effects of Solvent and Concentration on Periselectivity; 4.6.2 Effect of Diene/Dienophile Redox Potentials on Periselectivity; 4.6.3 Substituent and Steric Effects on Periselectivity; 4.6.4 Quantifying Periselectivity Through Ion Pair Association; 4.7 Endo/Exo Selectivity; 4.7.1 Effects of Secondary Orbital Interaction and Solvents on Endo/Exo Selectivity; 4.7.2 Effect of Sensitizer on Endo/Exo Selectivity; 4.7.3 Ion Pairs and Endo/Exo Selectivities; 4.8 Conclusions; 5. The Stability of Carbon-Centered Radicals; 5.1 Introduction 327 $a5.1.1 The Consequences of Different Stability Definitions: How Stable Are Ethyl and Fluoromethyl Radicals? 330 $aCovers the most advanced computational and experimental methods for studying carbon-centered radical intermediates With its focus on the chemistry of carbon-centered radicals and radical cations, this book helps readers fully exploit the synthetic utility of these intermediates in order to prepare fine chemicals and pharmaceutical products. Moreover, it helps readers better understand their role in complex atmospheric reactions and biological systems. Thoroughly up to date, the book highlights the most advanced computational and experimental methods available for studying and using 410 0$aWiley Series of Reactive Intermediates in Chemistry and Biology 606 $aFree radicals (Chemistry) 606 $aCarbon, Activated 606 $aReactivity (Chemistry) 606 $aCations 615 0$aFree radicals (Chemistry) 615 0$aCarbon, Activated. 615 0$aReactivity (Chemistry) 615 0$aCations. 676 $a547.1224 701 $aForbes$b Malcolm D. E.$f1960-$0882912 801 0$bMiAaPQ 801 1$bMiAaPQ 801 2$bMiAaPQ 906 $aBOOK 912 $a9910828353703321 996 $aCarbon-centered free radicals and radical cations$91972365 997 $aUNINA