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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.

Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)

Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)

Vicinal or three-bond coupling is commonly observed between protons attached to adjacent carbons. Here, nuclear spin information is primarily transferred via electron spin interactions between adjacent C‑H bond orbitals. This generally favors the antiparallel arrangement of spins, so 3J values are usually positive.
The extent of coupling depends on the C‑C bond length, the two H‑C‑C angles, any electron-withdrawing substituents, and the dihedral angle between the...

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.

Thermal and Photochemical Electrocyclic Reactions: Overview

Thermal and Photochemical Electrocyclic Reactions: Overview

Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.

Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)

Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)

Two NMR-active nuclei bonded to a central atom can be involved in geminal or two-bond coupling. Geminal coupling is commonly seen between diastereotopic protons in chiral molecules and unsymmetrical alkenes, among others.
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...

Photochemical Electrocyclic Reactions: Stereochemistry

Photochemical Electrocyclic Reactions: Stereochemistry

The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation

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Related Experiment Video

Updated: Sep 28, 2025

Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-phosphinetriyltripiperidine]}palladium Under Mild Reaction Conditions

Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-phosphinetriyltripiperidine]}palladium Under Mild Reaction Conditions

Published on: March 20, 2014

Ni-electrocatalytic Csp³-Csp³ doubly decarboxylative coupling.

Benxiang Zhang¹, Yang Gao¹, Yuta Hioki¹

¹Department of Chemistry, Scripps Research, La Jolla, CA, USA.

|April 5, 2022

Summary

Doubly decarboxylative cross-coupling enables the formation of new carbon-carbon bonds by joining two different carboxylates using a mild nickel-electrocatalytic system. This advances organic synthesis by overcoming limitations of traditional methods.

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Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy

Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy

Published on: November 9, 2019

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Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-phosphinetriyltripiperidine]}palladium Under Mild Reaction Conditions

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Published on: March 20, 2014

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

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Published on: April 4, 2014

Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy

Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy

Published on: November 9, 2019

Area of Science:

Organic Chemistry
Electrochemistry
Catalysis

Background:

Carbon-carbon bond formation is crucial for synthesizing complex molecules.
Kolbe electrolysis, an old Csp3-Csp3 bond-forming reaction, has limited scope due to harsh oxidative conditions.
Traditional methods struggle with limitations in scope and functional group tolerance.

Purpose of the Study:

To develop a milder, more versatile method for C-C bond formation using carboxylates.
To overcome the limitations of traditional Kolbe electrolysis and cross-electrophile coupling.
To enable the synthesis of complex molecules through a novel cross-coupling strategy.

Main Methods:

Development of a mildly reductive nickel-electrocatalytic system.
Utilizing in situ generated redox-active esters from carboxylates.
Employing doubly decarboxylative cross-coupling for heterocoupling.

Main Results:

Successfully coupled primary, secondary, and tertiary redox-active esters.
Demonstrated a novel method for doubly decarboxylative cross-coupling.
Achieved a 73% reduction in overall step counts for synthesizing 32 known compounds.
The reaction tolerates a wide range of functional groups and is scalable.

Conclusions:

The Ni-electrocatalytic system provides a powerful new approach for C-C bond formation.
This method expands the synthetic utility of carboxylates in organic synthesis.
The doubly decarboxylative cross-coupling offers an operationally simple and efficient alternative to existing methods.