Chapter 15: Alcohols, Diols and Thiols

Reactions of RLi and RMgX with Esters
(review of Chapter 14)

Reaction type:  Nucleophilic Acyl Substitution then Nucleophilic Addition

Summary:

• Carboxylic esters, R'CO₂R'', react with 2 equivalents of organolithium or Grignard reagents to give tertiary alcohols.
• The tertiary alcohol contains 2 identical alkyl groups (see R)
• The reaction proceeds via a ketone intermediate which then reacts with the second equivalent of the organometallic reagent.
• Since the ketone is more reactive than the ester, the reaction cannot be used as a preparation of ketones.

• Reaction of RLi and RMgX with aldehydes and ketones
• Reaction of RLi and RMgX with epoxides
• Reaction of RLi and RMgX with carbon dioxide

REACTION OF RLi or RMgX WITH AN ESTER
Step 1: The nucleophilic C in the organometallic reagent adds to the electrophilic C in the polar carbonyl group of the ester. Electrons from the C=O move to the electronegative O creating an intermediate metal alkoxide complex.
Step 2: The tetrahedral intermediate collapses and displaces the alcohol portion of the ester as a leaving group, this produces an aldehyde as an intermediate.
Step 3: The nucleophilic C in the organometallic reagent adds to the electrophilic C in the polar carbonyl group of the ketone. Electrons from the C=O move to the electronegative O creating an intermediate metal alkoxide complex.
Step 4: This is the  work-up step, a simple acid/base reaction. Protonation of the alkoxide oxygen creates the alcohol product from the intermediate complex.

© Dr. Ian Hunt, Department of Chemistry