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α-Hydroxy Ketones via Reductive Coupling of Esters: Acyloin Condensation Overview

α-Hydroxy Ketones via Reductive Coupling of Esters: Acyloin Condensation Overview

The pinacol and McMurry reactions involve the reductive coupling of ketones or aldehydes. Similarly, the bimolecular reductive coupling of two ester molecules in the presence of sodium metal in an aprotic solvent yields an α-hydroxy ketone product. The α-hydroxy ketone is also called acyloin, so the reaction is referred to as ‘acyloin condensation.’

Vicinal Diols via Reductive Coupling of Aldehydes or Ketones: Pinacol Coupling Overview

Vicinal Diols via Reductive Coupling of Aldehydes or Ketones: Pinacol Coupling Overview

Wilhelm Rudolph Fittig discovered the pinacol coupling reaction in 1859. It is a radical dimerization reaction and involves the reductive coupling of aldehydes or ketones in the presence of hydrocarbon solvent to yield vicinal diols.

Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction

Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction

The radical dimerization of ketones or aldehydes gives vicinal diols through a pinacol coupling reaction. However, the behavior of titanium metals used for the reaction as a source of electrons is unusual. When the reaction is carried out in the presence of titanium, diols can be isolated at low temperatures. Else titanium further reacts with diols, forming alkenes through the McMurry reaction.

Aldol Condensation with β-Diesters: Knoevenagel Condensation

Aldol Condensation with β-Diesters: Knoevenagel Condensation

The Knoevenagel condensation is an aldol-type reaction involving the condensation of aldehydes or ketones with active methylene compounds such as β-diesters to produce substituted olefins.

Acid-Catalyzed Aldol Addition Reaction

Acid-Catalyzed Aldol Addition Reaction

The aldol reaction of a ketone under acidic conditions successfully forms an unsaturated carbonyl as the final product instead of an aldol. The acid-catalyzed aldol reaction is depicted in Figure 1.

C–C Bond Cleavage: Retro-Aldol Reaction

C–C Bond Cleavage: Retro-Aldol Reaction

The reverse of the aldol addition reaction is called the retro-aldol reaction. Here, the carbon–carbon bond in the aldol product is cleaved under acidic or basic conditions to form two molecules of carbonyl compounds. The mechanism of the reaction consists of three steps.
In the first step, as depicted in Figure 1, the base deprotonates the β-hydroxy ketone at the hydroxyl group to form an alkoxide ion.

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A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species

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Published on: August 16, 2018

Electroreductive Olefin-Ketone Coupling.

Pengfei Hu^1,2, Byron K Peters^1,2, Christian A Malapit^3,2

¹Department of Chemistry, Scripps Research, 10550 North Torrey Pines Road, La Jolla 92037, California, United States.

Journal of the American Chemical Society

|December 1, 2020

Summary

This summary is machine-generated.

This study introduces a novel electrochemical method where ketones act as nucleophiles to synthesize tertiary alcohols from olefins. This user-friendly technique offers a scalable and air/water-tolerant alternative to traditional Grignard additions.

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Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate

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Published on: June 21, 2017

Area of Science:

Organic Chemistry
Synthetic Methodology
Electrochemistry

Background:

Traditional Grignard addition to unactivated ketones is a cornerstone for synthesizing tertiary alcohols.
This method often requires strict anhydrous and anaerobic conditions, limiting its practical application.
Developing alternative, user-friendly synthetic routes remains a significant challenge in organic synthesis.

Purpose of the Study:

To present a novel, user-friendly approach for synthesizing tertiary alcohols from unactivated ketones and olefins.
To reverse the typical polarity disconnection, enabling ketones to act as nucleophiles.
To establish a scalable, chemoselective, and robust electrochemical method for this transformation.

Main Methods:

An electrochemical approach was employed to facilitate the nucleophilic addition of ketones to unactivated olefins.
The reaction was optimized for scope, scalability, and tolerance to air and water.
Mechanistic studies were conducted to elucidate the reaction pathway.

Main Results:

The developed electrochemical method successfully couples ketones with simple unactivated olefins to yield tertiary alcohols.
The reaction demonstrates broad scope, high chemoselectivity, and scalability.
The process is tolerant to air and water, simplifying experimental procedures.

Conclusions:

This work presents a significant advancement in synthetic organic chemistry by offering a user-friendly alternative to Grignard reactions.
The electrochemical method simplifies multistep synthesis and provides access to tertiary alcohols under mild conditions.
The intuitive mechanism, distinct from traditional reductants like SmI2, highlights the novelty of this approach.