Carboxylic Acids Reduction Mechanism

Aug 14, 2024

Reduction of Carboxylic Acids

Key Concepts

  • Reduction Process: The reduction of carboxylic acids to alcohols using lithium aluminum hydride (LiAlH₄) involves a decrease in the oxidation state of the carbon in the acid.
  • Alternative Reagent: Borane (BH₃) can also be used for this reduction and is more chemoselective.

Mechanism

Step 1: Acid-Base Reaction

  • Carboxylic Acid Formation: Start with the carboxylic acid, focusing on the acidic proton on the oxygen.
  • Lithium Aluminum Hydride: Acts as a strong base; a hydride ion (H⁻) is a hydrogen atom with two electrons.
  • Formation of Carboxylate Anion: Proton from the carboxylic acid is removed by the hydride, forming a carboxylate ion (negatively charged oxygen) and hydrogen gas (H₂).

Step 2: Formation of Aldehyde

  • Carboxylate Anion and Aluminum Hydride Reaction:
    • Formation of bond between oxygen and aluminum (AlH₃), and between carbon and hydrogen.
    • Results in a tetrahedral carbon structure, forming an aldehyde.

Step 3: Reduction to Alcohol

  • Further Reduction:
    • Excess lithium aluminum hydride reduces the aldehyde to an alcohol.
    • Hydride ion attacks the carbonyl carbon, turning the aldehyde into an alcohol.
  • Protonation:
    • The alkoxide ion (formed during reduction) is protonated to yield the alcohol as the product.

Application and Selectivity

Practice Problem

  • Example: Reduction of a compound with both a carboxylic acid and ketone group using LiAlH₄.
    • Both functional groups (carboxylic acid to primary alcohol and ketone to secondary alcohol) are reduced.

Borane as a Reducing Agent

  • Chemoselectivity: Borane selectively reduces only the carboxylic acid group.
  • Application: Useful when selective reduction is needed to prevent reduction of other functional groups such as ketones.

Conclusion

  • Lithium aluminum hydride is effective in reducing carboxylic acids to alcohols, but is less selective compared to borane, which is preferred for its chemoselectivity in certain situations.