Related Experiment Video
Updated: Jul 29, 2026

Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes
Published on: September 8, 2013
Enantioselective formal hydration of alpha,beta-unsaturated imides by Al-catalyzed conjugate addition of oxime
Christopher D Vanderwal1, Eric N Jacobsen
1Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138, USA.
This study introduces an efficient catalytic method for asymmetric conjugate addition using salicylaldoxime, enabling enantioselective hydration of olefins. This breakthrough offers a novel route for synthesizing complex molecules, including polyketide natural products.
Area of Science:
- Organic Chemistry
- Catalysis
- Asymmetric Synthesis
Background:
- Alpha,beta-unsaturated imides are important synthetic intermediates.
- Enantioselective synthesis of complex organic molecules remains a significant challenge.
Purpose of the Study:
- To develop an efficient and highly enantioselective method for the formal hydration of alpha,beta-unsaturated imides.
- To explore the conjugate addition of oxygen-centered nucleophiles to electron-deficient olefins.
Main Methods:
- Utilized a (salen)Aluminum catalyst for asymmetric conjugate addition.
- Employed salicylaldoxime as the nucleophile.
- Investigated the reaction with chiral, nonracemic substrates.
Main Results:
- Achieved an efficient and highly enantioselective two-step formal hydration.
- Demonstrated the first enantioselective conjugate addition of an oxygen nucleophile to unsaturated carboxylic acid derivatives.
- Observed high catalyst-induced diastereoselectivity with chiral substrates.
Conclusions:
- The developed method provides a powerful new tool for asymmetric synthesis.
- The reaction's high diastereoselectivity highlights its potential for synthesizing polyketide natural products.
- This work expands the scope of enantioselective conjugate addition reactions.
More Related Videos
Related Concept Videos
Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration
Alkynes to Aldehydes and Ketones: Acid-Catalyzed Hydration
Analogous to alkenes, alkynes also undergo acid-catalyzed hydration. While the addition of water to an alkene gives an alcohol, hydration of alkynes produces different products such as aldehydes and ketones.
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
Aldehydes and Ketones with Water: Hydrate Formation
The formation of hydrates is a reversible reaction. Hydrate formation is influenced by steric and electronic factors accompanying the alkyl substituents on the carbonyl group: The rate of hydrate formation increases with a decrease in the number of alkyl groups attached to the carbonyl carbon. Hence,...
Conjugate Addition to α,β-Unsaturated Carbonyl Compounds
Conjugate Addition of Enolates: Michael Addition

