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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.

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.’

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.

Thermal Electrocyclic Reactions: Stereochemistry

Thermal Electrocyclic Reactions: Stereochemistry

The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.

[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction

[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction

The Diels–Alder reaction is an example of a thermal pericyclic reaction between a conjugated diene and an alkene or alkyne, commonly referred to as a dienophile. The reaction involves a concerted movement of six π electrons, four from the diene and two from the dienophile, forming an unsaturated six-membered ring. As a result, these reactions are classified as [4+2] cycloadditions.

Esters to Alcohols: Hydride Reductions

Esters to Alcohols: Hydride Reductions

Esters are reduced to primary alcohols when treated with a strong reducing agent like lithium aluminum hydride. The reaction requires two equivalents of the reducing agent and proceeds via an aldehyde intermediate.
Lithium aluminum hydride is a source of hydride ions and functions as a nucleophile. The mechanism proceeds in three steps. Firstly, the nucleophilic hydride ion attacks the carbonyl carbon of the ester to form a tetrahedral intermediate. Subsequently, the carbonyl group re-forms,...

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Updated: Jun 10, 2025

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

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

Published on: June 21, 2017

電気誘導による還元性および減光性アルケネ-アルデヒド結合

Liam J Franov¹, Tayla L Wilsdon¹, Milena L Czyz¹

¹School of Chemistry, The University of Melbourne, Parkville, Victoria 3010, Australia.

Journal of the American Chemical Society

|October 17, 2024

まとめ

この要約は機械生成です。

この研究は,アルケンとヘテロアレンをアルデヒドと結合させる新しい電気化学的方法を導入し,多様なC ((sp3) 混合アルコールを生成します. この触媒のないアプローチは,複雑な酸素基の合成のための現在の方法の限界を克服します.

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Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols

Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols

Published on: April 4, 2014

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

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

Published on: August 16, 2018

関連する実験動画

Last Updated: Jun 10, 2025

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

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

Published on: June 21, 2017

Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols

Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols

Published on: April 4, 2014

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

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

Published on: August 16, 2018

科学分野:

有機化学
電気化学
合成方法論

背景:

アルケンとアルデヒドの直接結合は,基板の耐性および機能群の互換性の制限のために困難です.
アルデヒドとのC-Cπ結合の既存の方法は,複雑な分子環境においてしばしば制限されている.

研究の目的:

単純なアルケーン,ヘテロアレン,活性化されていないアリファートアルデヒドの直接結合のための効率的で多用途な方法を開発する.
簡単に入手可能な原料から様々なC ((sp3) 混合アルコールを合成することを可能にします.

主な方法:

電気化学的に誘導されたC-C π結合の迅速な交互の極性 (rAP) 電解を利用した.
還元結合の過程で使用された触媒のない条件.
ラジカルアニオンの生成と反応性を研究した.

主要な成果:

アルケンとヘテロアレンとアリファティックアルデヒドの直接結合が達成され,様々なC ((sp3) 混合アルコールが得られる.
rAP電解を用いたオレフィン基アニオンの化学選択生成が実証されている.
ヘテロサイクリック化合物の前例のない還元性・オロマティブ機能化が報告されています.

結論:

開発されたrAP電解プロトコルは,多用途で効率的なC ((sp3) 豊富な酸素化された構造物への経路を提供します.
この触媒のない方法は,有機合成のための還元結合反応の範囲を拡大します.
シンプルな原料から構造的に多様なアルコール製品への直接的なアクセスを提供します.