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Related Concept Videos

Stereochemical Effects of Enolization01:12

Stereochemical Effects of Enolization

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The chiral α-carbon of the carbonyl compound is the stereocenter of the molecule. As shown in the figure below, when such a carbonyl compound undergoes racemization under an acidic or basic condition, an achiral enol is formed.
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Reactivity of Enols01:18

Reactivity of Enols

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Enols are a class of compounds where a hydroxyl group is attached to a carbon–carbon double bond, which implies that it is a vinyl alcohol. A carbonyl compound with an α hydrogen undergoes keto–enol tautomerism and remains in equilibrium with its tautomer, the enol form. Usually, the keto tautomer is present in a higher concentration than the enol tautomer due to the higher bond energy of C=O compared to C=C. Moreover, the direction of the keto–enol equilibrium is...
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Regioselective Formation of Enolates01:33

Regioselective Formation of Enolates

2.5K
As depicted in the figure below, the unsymmetrical ketones can form two possible enolates:  less substituted or more substituted enolates. Usually, the thermodynamic enolates are formed from the more substituted α-carbon atom, while the kinetic enolates are formed faster by deprotonation from the less substituted position. The thermodynamic enolates have lower energy, so they are  more stable. But the energy required to form kinetic enolates is less.
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Alkylation of β-Ketoester Enolates: Acetoacetic Ester Synthesis01:07

Alkylation of β-Ketoester Enolates: Acetoacetic Ester Synthesis

3.2K
Acetoacetic ester synthesis is a method to obtain ketones from alkyl halides and β-keto esters. The reaction occurs in the presence of an alkoxide base that abstracts the acidic proton of the β-keto esters. The step results in an enolate ion which is doubly stabilized. The enolate then reacts with an alkyl halide via the SN2 process to produce an alkylated ester intermediate with a new C–C bond. The hydrolysis of the intermediate, followed by acidification, results in an...
3.2K
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation02:17

Reduction of Alkenes: Asymmetric Catalytic Hydrogenation

3.2K
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
3.2K
Alkylation of β-Diester Enolates: Malonic Ester Synthesis01:14

Alkylation of β-Diester Enolates: Malonic Ester Synthesis

3.3K
Malonic ester synthesis is a method to obtain α substituted carboxylic acids from ꞵ-diesters such as diethyl malonate and alkyl halides.
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Updated: May 19, 2025

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
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Dynamic Kinetic Asymmetric Hydroacylation: Racemization by Soft Enolization.

Mengfei Xu1, Stephanie A Corio2, Josephine M Warnica1

  • 1Department of Chemistry, University of California, Irvine, California 92697, United States.

Journal of the American Chemical Society
|April 29, 2025
PubMed
Summary
This summary is machine-generated.

This study introduces a dynamic kinetic asymmetric transformation (DyKAT) for creating valuable 1,4-ketoamides from aldehydes. Rh-catalyzed hydroacylation achieves high selectivity, offering a novel stereoconvergent C-C bond-forming strategy.

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Area of Science:

  • Organic Chemistry
  • Catalysis
  • Asymmetric Synthesis

Background:

  • Dynamic kinetic asymmetric transformation (DyKAT) enables the conversion of racemic starting materials into enantiomerically enriched products.
  • Intermolecular hydroacylation is a powerful C-C bond-forming reaction, but its application in DyKAT remains underexplored.
  • Stereoconvergent catalysis aims to maximize the efficiency of chiral synthesis by converting multiple stereocenters simultaneously.

Purpose of the Study:

  • To develop a novel dynamic kinetic asymmetric transformation (DyKAT) for the enantioselective synthesis of 1,4-ketoamides.
  • To investigate the Rh-catalyzed intermolecular hydroacylation of racemic aldehydes with acrylamides.
  • To elucidate the mechanism, including the aldehyde racemization pathway, using DFT and experimental studies.

Main Methods:

  • Dynamic kinetic asymmetric transformation (DyKAT)
  • Rhodium-catalyzed hydroacylation
  • Intermolecular reaction
  • DFT calculations
  • Kinetic resolution

Main Results:

  • Successful DyKAT of racemic aldehydes with acrylamides using Rh-catalysis.
  • High enantio- and diastereoselectivity achieved in the formation of 1,4-ketoamides.
  • Identification of an unexpected Rh-catalyzed pathway for aldehyde racemization.
  • Demonstration of a pioneering kinetic resolution via intermolecular hydroacylation.

Conclusions:

  • This work establishes a novel DyKAT for synthesizing 1,4-ketoamides with excellent stereocontrol.
  • The findings contribute significantly to the field of stereoconvergent catalysis and C-C bond construction.
  • The mechanistic insights provide a foundation for further development of related catalytic systems.