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Related Concept Videos

Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)01:22

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 involved orbitals. The...
¹H NMR: Long-Range Coupling01:27

¹H NMR: Long-Range Coupling

The coupling interactions of nuclei across four or more bonds are usually weak, with J values less than 1 Hz. While these are usually not observed in spectra, the presence of multiple bonds along the coupling pathway can result in observable long-range coupling.
In alkenes, spin information is communicated via σ–π overlap, as seen in allylic (four-bond) and homoallylic (five-bond) couplings. These coupling interactions are stronger when the σ bond is parallel to the alkene π orbitals.
Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)01:20

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...
Thermal Electrocyclic Reactions: Stereochemistry01:17

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.
β-Dicarbonyl Compounds via Crossed Claisen Condensations01:18

β-Dicarbonyl Compounds via Crossed Claisen Condensations

Crossed Claisen condensations are base-promoted reactions between two different ester molecules producing β-dicarbonyl compounds. The reaction involving esters, with both containing α hydrogen, results in a mixture of four different products that are difficult to isolate. This reduces the synthetic utility of the reaction.
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry01:28

Diels–Alder Reaction Forming Cyclic Products: Stereochemistry

The Diels–Alder reaction is one of the robust methods for synthesizing unsaturated six-membered rings. The reaction involves a concerted cyclic movement of six π electrons: four π electrons from the diene and two π electrons from the dienophile.

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Related Experiment Video

Updated: Jun 24, 2026

Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols
10:12

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

Published on: April 4, 2014

Stereoretentive decarbonylative C(sp3)-C(sp3) cross-coupling.

Zhidao Huang1, Tianrui Wu1, Zehao Yuan1

  • 1Department of Chemistry, University of Wisconsin-Madison, Madison, WI, USA.

Nature
|June 22, 2026
PubMed
Summary
This summary is machine-generated.

This study introduces a novel catalytic method for stereocontrolled C(sp3)-C(sp3) bond formation. The metallo-Curtius strategy enables enantioselective cross-coupling reactions using readily available chiral building blocks.

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

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Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions
11:44

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

Published on: March 20, 2014

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Last Updated: Jun 24, 2026

Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols
10:12

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

Published on: April 4, 2014

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

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Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions
11:44

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

Published on: March 20, 2014

Area of Science:

  • Organic Chemistry
  • Catalysis
  • Synthetic Methodology

Background:

  • Stereocontrolled C(sp3)-C(sp3) bond formation is crucial for drug discovery, yet remains challenging.
  • Existing enantioselective methods are limited by substrate availability and specialized precursors.
  • Stereospecific oxidative addition of abundant chiral alkyl electrophiles is a significant unmet need.

Purpose of the Study:

  • To develop a catalytic strategy for stereospecific C(sp3)-C(sp3) bond formation.
  • To utilize easily accessible chiral starting materials like amino acid and alpha-hydroxy acid derivatives.
  • To establish a new mechanistic foundation for stereospecific cross-coupling reactions.

Main Methods:

  • A catalytic strategy inspired by the Curtius rearrangement.
  • Formation of chiral alkylnickel intermediates via stereoretentive decarbonylation.
  • Stereoretentive cross-electrophile coupling with alkyl radicals at low temperatures (22-40 °C).

Main Results:

  • Demonstrated a novel catalytic approach for stereocontrolled C(sp3)-C(sp3) bond formation.
  • Successfully coupled versatile chiral alkylnickel intermediates with alkyl radicals.
  • Achieved formation of diastereomers inaccessible by stereoselective radical mechanisms.

Conclusions:

  • The developed "metallo-Curtius" strategy provides a straightforward route to stereocontrolled C(sp3)-C(sp3) bonds.
  • This method expands the scope of enantioselective cross-coupling reactions.
  • Lays the groundwork for future stereospecific cross-coupling methodologies.