General methods for stereocontrolled synthesis: partial synthesis, resolution, chiral pool, asymmetric synthesis: optically active reagents, auxiliars and catalysts. Applications in synthesis.
Retrosynthetic Analysis: key bonds, key disconnections
Baldwin Rules for ring closure: trajectories and orbital overlap
Conformation and Reactivity
Small ring systems: conformation and chemistry in 3–5 membered rings
Medium ring systems: conformation and chemistry in 6–8 membered rings. Anomeric effect.
Directed reactions (epoxidations, hydroboration, oxymercuration)
Acyclic systems: A1,3 and A1,2 allylic strain
Diastereoselective additions to acyclic carbonyl compounds (Felkin-Ahn, chelate model, polar model)
Enolate: structural features. Stereocontrolled synthesis (B-enolates). Reactivity in non-aldol
Relative stereochemistry (E vs Z enolate = anti vs. syn).
Ordered transition states: Traxler-Zimmermann and eclipsed model
Relative stereochemistry of three stereocenters: α-substituent in the enolate.
α-substituent in the electrophile
Absolute stereochemistry: Evans, Crimmins, Ti-enolates = chiral auxiliars
Mukaiyama Aldol Reaction
Chiral catalysts (B-Corey, Proline: Organocatalysis)
-Diels-Alder: Synthetic Equivalents and Ring strain. Synthetic Application. Asymmetric Variants.
-1,3-Dipolar cycloadditions. Synthetic applications.
- Ene and Oxo-ene reactions
- Claisen, Cope, other sigmatropic rearrangements (stereocontrol and Synthetic Applications)
Other topics: Asymmetric Olefin metathesis. Alkyne metathesis