The Anomeric Effect and Related Stereoelectronic Effects at Oxygen

Inhaltsverzeichnis

• A. Stereoelectronic Effects on Structure.
• 1. Introduction.
• 2. The Anomeric Effect.
• 3. The Reverse Anomeric Effect.
• 4. The Exo-Anomeric Effect.
• 5. The Generalised Anomeric Effect.
• a. Sulphur Compounds.
• b. Transmission through Phosphorus.
• c. Transmission through Sulphur.
• 6. The Gauche Effect.
• B. The Electronic Basis of the Effects.
• 2. The Status of Lone Pair Electrons.
• a. Evidence from Hydrogen-bonding.
• b. Electron Density Measurements.
• 3. Calculations on X? Y Systems.
• 4. Effects on Bond Lengths and Angles.
• 5. Effects in Furanoses.
• 6. The Stereoelectronic Basis of the Anomeric Effect.
• a. The Structure of CH2F2.
• b. Bonding in ROCH2X.
• c. Bonding and Restricted Rotation in Dimethoxymethane.
• d. The Generalised Anomeric Effect.
• e. The Reverse Anomeric Effect.
• f. The Exo-Anomeric Effect.
• 7. Related Stereoelectronic Effects.
• a. The Anomeric Effect at sp2 centres.
• b. The Gauche Effect.
• C. Stereoelectronic Effects on Reactivity: The Kinetic Anomeric Effect.
• a. The Use of sp3-hybrid Lone Pairs.
• b. The Stereoelectronic Basis of the Kinetic Anomeric Effect.
• 2. Reactions of the Acetal Group.
• a. Acetal Hydrolysis.
• b. Acetal Formation.
• c. Acetal Oxidation.
• 3. The Hydrolysis of Orthoesters.
• a. Hemiorthoesters.
• 4. Carbonyl-Oxygen Exchange Reactions of Esters and Amides.
• 5. The Hydrolysis of Imidate Esters: Stereoelectronic Effects at Oxygen and Nitrogen.
• 6. Reactions of Phosphate Esters.
• 7. Radical Reactions.
• 8. Enzyme Reactions.
• D. Appendix.
• 1. Canonical Lone Pair Description.
• 2. Hybrid Lone Pair Description.
• E. References.
• F. Subject Index.