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Understanding Retro-Aldol Reactions and Retrosynthesis

Feb 27, 2025

Retro-Aldol Reactions and Retrosynthesis

Introduction

  • Retrosynthesis involves thinking about chemical reactions in reverse.
  • Focus on retro-aldol reactions, which are the reverse of aldol condensations.
  • Example used: cinnamaldehyde, which through retro-aldol reaction with sodium carbonate forms benzaldehyde and acetaldehyde.

Cinnamaldehyde to Benzaldehyde and Acetaldehyde

  • Cinnamaldehyde: Smells like cinnamon.
  • Benzaldehyde: Smells like almonds.
  • Mechanism Overview:
    • Identify alpha and beta carbons surrounding the carbonyl group.
    • Break the double bond, converting cinnamaldehyde into its component molecules.
    • Add H2 (hydrogens) to the alpha carbon and water (H2O) to the beta carbon.

Retrosynthesis

  • Useful for synthesizing enones and enals by thinking about retro-aldol reactions.
  • Example given for synthesizing an enone:
    • Identify alpha and beta carbons in the target enone.
    • Break double bond between these carbons.
    • Formulate starting ketone and aldehyde for synthesis.
    • Reaction Conditions: Use sodium hydroxide in water and ethanol for aldol condensation.

Directed Aldol Addition

  • When target compound is an aldol, not an enone or enal.
  • Identify alpha and beta carbons and break the bond connecting them.
  • Use LDA to form a lithium enolate for controlled addition.
  • Example given for synthesizing an aldol:
    • Start with ketone, use LDA to form an enolate, then add aldehyde.
    • Workup with water to obtain the aldol product.

Intramolecular Aldol Condensation

  • Example of synthesizing a cyclic compound via intramolecular aldol condensation.
  • Steps:
    • Identify alpha and beta carbons in the ring.
    • Break the internal double bond and identify carbons involved.
    • Use a base to facilitate the intramolecular condensation.

Conclusion

  • Retro-aldol reactions and retrosynthesis offer strategic ways to approach synthesis problems by breaking down complex molecules into simpler precursors.
  • Upcoming discussions on intramolecular aldol condensation in further detail.