# Synthesis of Sterically Congested Carbonyl Compounds via an ipso-Selective Sulfonium Rearrangement

**Authors:** Immo Klose, Christian Knittl-Frank, Nicolas G.-Simonian, Boris Maryasin, Daniel Kaiser, Nuno Maulide

PMC · DOI: 10.1021/jacs.5c13777 · Journal of the American Chemical Society · 2025-10-08

## TL;DR

A new method is introduced for making crowded carbonyl compounds using a sulfonium rearrangement, which works well where traditional methods fail.

## Contribution

The ipso-selective sulfonium rearrangement provides a novel, metal-free route for synthesizing sterically congested α-arylated carbonyl compounds.

## Key findings

- The method enables synthesis of α-arylated carbonyl compounds that are difficult to make via traditional cross-coupling.
- The sulfonium-based rearrangement is robust against steric hindrance.
- This approach is orthogonal to metal-catalyzed strategies.

## Abstract

Despite the success
of metal-catalyzed
cross-coupling strategies
to assemble a variety of C–C bonds, the synthesis of sterically
congested α-arylated carbonyl compounds remains a difficult
task. Herein, we present an ipso-rearrangement approach
relying on electron redistribution in sulfonium intermediates. This
modular method enables the synthesis of a variety of α-arylated
carbonyl compounds and is orthogonal to traditional metal-catalyzed
cross-coupling strategies. More importantly, it demonstrated remarkable
robustness toward steric hindrance and allowed us to efficiently forge
congested C–C bonds.

## Full-text entities

- **Chemicals:** C (MESH:D002244), metal (MESH:D008670), Carbonyl Compounds (-)

## Full text

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## Figures

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## References

94 references — full list in the complete paper: https://tomesphere.com/paper/PMC12550846/full.md

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Source: https://tomesphere.com/paper/PMC12550846