Organic Mechanisms. Xiaoping Sun

      

      Table of Contents

      1  COVER

      2  TITLE PAGE

      3  COPYRIGHT PAGE

      4  PREFACE

      5  FIRST EDITION PREFACE

      6  ABOUT THE COMPANION WEBSITE

      7  1 FUNDAMENTAL PRINCIPLES 1.1 REACTION MECHANISMS AND THEIR IMPORTANCE 1.2 ELEMENTARY (CONCERTED) AND STEPWISE REACTIONS 1.3 MOLECULARITY 1.4 KINETICS 1.5 THERMODYNAMICS 1.6 THE TRANSITION STATE 1.7 ELECTRONIC EFFECTS AND HAMMETT EQUATION 1.8 THE MOLECULAR ORBITAL THEORY 1.9 ELECTROPHILES/NUCLEOPHILES VERSUS ACIDS/BASES 1.10 ISOTOPE LABELING 1.11 ENZYMES: BIOLOGICAL CATALYSTS 1.12 THE GREEN CHEMISTRY METHODOLOGY REFERENCES

      8  2 THE ALIPHATIC C─H BOND FUNCTIONALIZATION 2.1 ALKYL RADICALS: BONDING AND THEIR RELATIVE STABILITY 2.2 RADICAL HALOGENATIONS OF THE C─H BONDS ON SP³‐HYBRIDIZED CARBONS: MECHANISM AND NATURE OF THE TRANSITION STATES 2.3 ENERGETICS OF THE RADICAL HALOGENATIONS OF ALKANES AND THEIR REGIOSELECTIVITY 2.4 KINETICS OF RADICAL HALOGENATIONS OF ALKANES 2.5 RADICAL INITIATORS 2.6 TRANSITION‐METAL‐COMPOUNDS CATALYZED ALKANE C─H BOND ACTIVATION AND FUNCTIONALIZATION 2.7 SUPERACIDS CATALYZED ALKANE C─H BOND ACTIVATION AND FUNCTIONALIZATION 2.8 NITRATION OF THE ALIPHATIC C─H BONDS VIA THE NITRONIUM NO₂⁺ ION 2.9 PHOTOCHEMICAL AND THERMAL C─H BOND ACTIVATION BY THE OXIDATIVE URANYL UO₂²⁺(VI) CATION 2.10 ENZYME CATALYZED ALKANE C─H BOND ACTIVATION AND FUNCTIONALIZATION: BIOCHEMICAL METHODS REFERENCES

      9  3 FUNCTIONALIZATION OF THE ALKENE C=C BOND BY ELECTROPHILIC ADDITIONS 3.1 MARKOVNIKOV ADDITIONS VIA INTERMEDIATE CARBOCATIONS 3.2 ELECTROPHILIC ADDITION OF HYDROGEN HALIDES TO CONJUGATED DIENES 3.3 NON‐MARKOVNIKOV RADICAL ADDITION 3.4 HYDROBORATION: CONCERTED, NON‐MARKOVNIKOV syn‐ADDITION 3.5 TRANSITION‐METAL CATALYZED HYDROGENATION OF THE ALKENE C=C BOND (syn‐ADDITION) 3.6 HALOGENATION OF THE ALKENE C=C BOND (ANTI‐ADDITION): MECHANISM AND ITS STEREOCHEMISTRY REFERENCES

      10  4 FUNCTIONALIZATION OF THE ALKENE C=C BOND BY CYCLOADDITION REACTIONS 4.1 CYCLOADDITION OF THE ALKENE C=C BOND TO FORM THREE‐MEMBERED RINGS 4.2 CYCLOADDITIONS TO FORM FOUR‐MEMBERED RINGS 4.3 DIELS–ALDER CYCLOADDITIONS OF THE ALKENE CC BOND TO FORM SIX‐MEMBERED RINGS 4.4 1,3‐DIPOLAR CYCLOADDITIONS OF THE C=C AND OTHER MULTIPLE BONDS TO FORM FIVE‐MEMBERED RINGS 4.5 OTHER PERICYCLIC REACTIONS 4.6 DIELS–ALDER CYCLOADDITIONS IN WATER: THE GREEN CHEMISTRY METHODS 4.7 BIOLOGICAL APPLICATIONS REFERENCES

      11  5 THE AROMATIC C─H BOND FUNCTIONALIZATION AND RELATED REACTIONS 5.1 AROMATIC NITRATION: ALL REACTION INTERMEDIATES AND FULL MECHANISM FOR THE AROMATIC C─H BOND SUBSTITUTION BY NITRONIUM (NO₂⁺) AND RELATED ELECTROPHILES 5.2 MECHANISMS AND SYNTHETIC UTILITY FOR AROMATIC C─H BOND SUBSTITUTIONS BY OTHER RELATED ELECTROPHILES 5.3 THE IRON (III) CATALYZED ELECTROPHILIC AROMATIC C─H BOND SUBSTITUTION 5.4 THE ELECTROPHILIC AROMATIC C─H BOND SUBSTITUTION REACTIONS VIA S_N1 and S_N2 MECHANISMS 5.5 SUBSTITUENT EFFECTS ON THE ELECTROPHILIC AROMATIC SUBSTITUTION REACTIONS 5.6 ISOMERIZATIONS EFFECTED BY THE ELECTROPHILIC AROMATIC SUBSTITUTION REACTIONS 5.7 ELECTROPHILIC SUBSTITUTION REACTIONS ON THE AROMATIC CARBON─METAL BONDS: MECHANISMS AND SYNTHETIC APPLICATIONS 5.8 NUCLEOPHILIC AROMATIC SUBSTITUTION VIA A BENZYNE (ARYNE) INTERMEDIATE: FUNCTIONAL GROUP TRANSFORMATIONS ON AROMATIC RINGS 5.9 NUCLEOPHILIC AROMATIC SUBSTITUTION VIA AN ANIONIC MEISENHEIMER COMPLEX 5.10