Organic Mechanisms and Named Reactions

100 lessons, pages 2721–2820.

  1. Foundations of Organic Mechanisms — Electron flow and bond changes
  2. Curved Arrow Notation — Drawing electron-pair movement
  3. Homolytic and Heterolytic Bond Cleavage — Radical and ionic bond breaking
  4. Formal Charge in Mechanisms — Bookkeeping charged intermediates
  5. Electrophiles and Nucleophiles — Identifying donors and acceptors
  6. Acids and Bases in Organic Chemistry — Proton transfer as a mechanism
  7. Inductive Effects — Sigma-bond electron influences
  8. Resonance Effects — Conjugated electron delocalization
  9. Hyperconjugation — Adjacent sigma-bond stabilization
  10. Steric Effects — Crowding in transition states
  11. Reaction Coordinates and Activation Energy — Intermediates and rate barriers
  12. Thermodynamics versus Kinetics — Product stability versus pathway speed
  13. Reactive Intermediates Overview — Cations, anions, radicals and carbenes
  14. Carbocation Stability — Substitution and resonance effects
  15. Carbocation Rearrangements — Hydride and alkyl shifts
  16. Carbanion Stability — Electron withdrawal and hybridization
  17. Radical Stability — Resonance and radical substitution
  18. Carbenes and Nitrenes Introduction — Electron-deficient intermediates
  19. Leaving Group Ability — Departing fragment stability
  20. Nucleophilicity versus Basicity — Carbon attack versus proton removal
  21. Solvent Effects in Mechanisms — Protic, aprotic and ion-pair effects
  22. SN2 Reaction Coordinate — Concerted backside substitution
  23. SN2 Kinetics — Two-reactant rate dependence
  24. SN2 Stereochemistry — Inversion and configuration
  25. SN1 Reaction Coordinate — Carbocation formation and capture
  26. SN1 Kinetics — Ionization-limited rate
  27. SN1 Stereochemistry — Two-face attack and ion pairs
  28. SN1 Rearrangement Problems — Tracing shifts before capture
  29. Comparing SN1 and SN2 — Structure, solvent, rate and stereochemistry
  30. E2 Reaction Coordinate — Concerted beta-proton removal
  31. E2 Stereochemistry — Antiperiplanar stereospecificity
  32. E2 in Cyclohexanes — Trans-diaxial chair geometry
  33. E1 Reaction Coordinate — Carbocation then deprotonation
  34. E1 Rearrangement and Products — Shifts and alkene isomers
  35. Substitution and Elimination Networks — SN1, SN2, E1 and E2 competition
  36. Zaitsev and Hofmann Selectivity — Substitution versus base access
  37. E1cB Elimination — Conjugate-base intermediate
  38. Addition to Alkenes Overview — Electrophiles across pi bonds
  39. Hydrogen Halide Addition — Orientation and peroxide exception
  40. Halogen Addition to Alkenes — Halonium ions and anti addition
  41. Halohydrin Formation — Water attack on halonium ions
  42. Acid-Catalyzed Alkene Hydration — Markovnikov alcohol formation
  43. Hydroboration–Oxidation — Anti-Markovnikov syn hydration
  44. Oxymercuration–Demercuration — Markovnikov hydration without free cation
  45. Catalytic Hydrogenation — Surface-mediated hydrogen addition
  46. Alkene Oxidation Overview — Epoxidation, dihydroxylation and cleavage
  47. Epoxide Formation — Peracid oxygen transfer
  48. Epoxide Ring Opening — Acidic and basic ring opening
  49. Ozonolysis of Alkenes — Cleaving C=C to carbonyls
  50. Alkyne Addition Mechanisms — Addition to triple bonds
  51. Alkyne Hydration and Tautomerism — Enol to carbonyl conversion
  52. Alkyne Hydroboration–Oxidation — Terminal aldehyde formation
  53. Acetylide Chemistry — Carbon–carbon bond formation
  54. Electrophilic Aromatic Substitution Overview — Sigma complex and aromaticity restoration
  55. Aromatic Nitration — Nitronium generation and attack
  56. Aromatic Sulfonation — Sulfonic-acid installation
  57. Aromatic Halogenation — Lewis-acid halogen activation
  58. Friedel–Crafts Alkylation — Carbon electrophiles and rearrangements
  59. Friedel–Crafts Acylation — Acylium electrophile and ketones
  60. Activating and Deactivating Ring Groups — Rate effects of substituents
  61. Ortho, Meta and Para Directing — Positional electronic selectivity
  62. Multiple Substituents on Aromatic Rings — Combining directing and steric effects
  63. Nucleophilic Aromatic Substitution — Activated aryl addition–elimination
  64. Benzyne Pathway Introduction — Elimination–addition under strong base
  65. Carbonyl Polarity and Addition — Electrophilic carbonyl carbon
  66. Hydride Reduction of Carbonyls — Aldehyde and ketone reduction
  67. Grignard Addition to Carbonyls — Carbon–carbon bonds and alcohols
  68. Cyanohydrin Formation — Cyanide addition and protonation
  69. Acetal and Hemiacetal Formation — Alcohol addition to carbonyls
  70. Imine Formation — Amine condensation and dehydration
  71. Enamine Formation — Secondary-amine carbonyl condensation
  72. Carbonyl Addition Stereochemistry — Facial attack at C=O
  73. Carboxylic Acid Derivative Reactivity — Acyl substitution and leaving groups
  74. Nucleophilic Acyl Substitution — Addition–elimination at acyl carbon
  75. Acid Chloride Reactions — High-reactivity acyl transfer
  76. Esterification and Hydrolysis — Reversible acid-catalyzed exchange
  77. Base-Promoted Ester Hydrolysis — Saponification and carboxylate
  78. Amide Formation and Hydrolysis — Acyl nitrogen bond chemistry
  79. Enols and Enolates — Alpha-carbon acidity and tautomerism
  80. Aldol Addition — Enolate attack on carbonyl
  81. Aldol Condensation — Dehydration to conjugated products
  82. Claisen Condensation — Ester enolate acylation
  83. Cannizzaro Reaction — Non-enolizable aldehyde disproportionation
  84. Haloform Reaction — Methyl-ketone cleavage
  85. Michael Addition — Conjugate carbon nucleophile addition
  86. Robinson Annulation — Michael addition plus aldol cyclization
  87. Aromatic Diazonium Formation — Aromatic amine nitrosation
  88. Sandmeyer and Diazonium Replacements — Diazonium halide substitution
  89. Azo Coupling — Electrophilic azo bond formation
  90. Williamson Ether Synthesis — Alkoxide attack on alkyl halide
  91. Wurtz and Related Couplings — Metal-assisted halide coupling
  92. Kolbe–Schmitt Reaction — Phenoxide carboxylation
  93. Reimer–Tiemann Reaction — Phenol formylation
  94. Pinacol Rearrangement — Vicinal diol rearrangement
  95. Beckmann Rearrangement — Oxime to amide conversion
  96. Hofmann Bromamide Rearrangement — Amide to shorter amine
  97. Baeyer–Villiger Oxidation — Oxygen insertion into ketones
  98. Mechanism Evidence and Problem Solving — Rate, isotope and stereochemical evidence
  99. Organic Mechanisms Review — Integrating named reactions and electron flow
  100. Organic Synthesis Mechanism Audit — Checking charge, atoms and selectivity