Synthesis of Sterically Congested Carbonyl Compounds via an <i>ipso</i> -Selective Sulfonium Rearrangement

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 <i>ipso</i>-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.

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Publication Details

Journal
Journal of the American Chemical Society
Published
2025-10-08
DOI
https://doi.org/10.1021/jacs.5c13777
Primary Topic
Sulfur-Based Synthesis Techniques
Type
article
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article

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

Immo Klose, Christian Knittl‐Frank, Boris Maryasin, Daniel Kaiser et al.
Journal of the American Chemical Society
Sulfur-Based Synthesis Techniques
article

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

Immo Klose, Christian Knittl‐Frank, Boris Maryasin, Daniel Kaiser, Nuno Maulide, Nicolas G.-Simonian
article en

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 <i>ipso</i>-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.

Journal of the American Chemical SocietyVol. 147(42)
University of Vienna (AT)
Openalex Percentile: Top 79%
Sulfur-Based Synthesis Techniques
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Synthesis of Sterically Congested Carbonyl Compounds via an <i>ipso</i> -Selective Sulfonium Rearrangement — Immo Klose, Christian Knittl‐Frank, et al. · Journal of the American Chemical Society (2025) | TGRS Research Map | TGRS