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Related Experiment Video

Updated: May 19, 2026

Efficient Synthesis of All-Carbon Quaternary Centers via the Conjugate Addition of Functionalized Monoorganozinc Bromides

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Published on: May 26, 2019

Cation Sampling Enables Regiodivergent Distal Functionalization of Ketones.

Philipp Spieß¹, Miloš Vavrík¹, Jakob Frey¹

¹Institute of Organic Chemistry, University of Vienna, Währinger Straße 38, 1090 Vienna, Austria.

Journal of the American Chemical Society

|May 18, 2026

Summary

This study introduces a novel ketone-assisted cationic olefin isomerization for regiodivergent C-H functionalization. This approach enables selective C-heteroatom bond formation at challenging positions, overcoming limitations of metal-based methods.

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Area of Science:

Organic Chemistry
Catalysis
Synthetic Methodology

Background:

Catalytic olefin isomerization is crucial for C-H functionalization.
Existing metal-based methods struggle with regiodivergent outcomes and complex systems.
Distal Csp3-H functionalization remains a significant challenge in organic synthesis.

Purpose of the Study:

To develop a novel, metal-free approach for regiodivergent Csp3-H functionalization.
To enable site-selective formation of C-heteroatom bonds in previously inaccessible positions.
To overcome the limitations of current catalytic systems in achieving controlled regioselectivity.

Main Methods:

Leveraging cationic olefin isomerization.
Employing a ketone-assisted process termed 'cation sampling' for selectivity control.
Utilizing mechanistic studies to elucidate the reaction pathway involving oxocarbenium intermediates.

Main Results:

Achieved regiodivergent Csp3-H functionalization via cationic olefin isomerization.
Demonstrated site-selective C-heteroatom bond formation at challenging sp3-hybridized carbons.
Unlocked access to products not attainable with traditional metal-based methodologies.

Conclusions:

The developed method offers a conceptually distinct and effective strategy for regiodivergent C-H functionalization.
Ketone-assisted cation sampling provides precise control over regioselectivity.
This work expands the synthetic toolbox for creating complex organic molecules.