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Updated: Aug 1, 2026

Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Tandem chain extension-aldol reaction: syn selectivity with a zinc enolate
S Lai1, C K Zercher, J P Jasinski
1Department of Chemistry, University of New Hampshire, Durham, NH 03824, USA.
A novel zinc-mediated reaction efficiently converts beta-keto esters into valuable alpha-substituted-gamma-keto esters in a single step. This tandem chain extension-aldol process offers excellent control over stereochemistry for various substrates.
Area of Science:
- Organic Chemistry
- Synthetic Chemistry
Background:
- Beta-keto esters are versatile building blocks in organic synthesis.
- Developing efficient methods for their functionalization is crucial for accessing complex molecules.
Purpose of the Study:
- To develop a novel, efficient one-pot method for the synthesis of alpha-substituted-gamma-keto esters.
- To investigate the stereochemical outcomes of this new transformation.
Main Methods:
- A tandem chain extension-aldol reaction sequence was employed.
- The reaction was mediated by zinc.
- Substrates included beta-keto esters, amides, and imides.
Main Results:
- The reaction efficiently transformed beta-keto esters to alpha-substituted-gamma-keto esters.
- Diastereoselectivity was good to excellent.
- Syn stereochemistry was observed for beta-keto ester and amide substrates.
- Anti-stereochemistry was observed for beta-keto imide substrates.
Conclusions:
- A new, efficient zinc-mediated tandem reaction for synthesizing alpha-substituted-gamma-keto esters has been established.
- The reaction provides excellent diastereoselectivity, with predictable stereochemical outcomes based on substrate type.
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