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Shuttle Arylation by Rh(I) Catalyzed Reversible Carbon–Carbon Bond Activation of Unstrained Alcohols

submitted on 21.10.2020, 14:17 and posted on 22.10.2020, 07:08 by Marius D. R. Lutz, Valentina C. M. Gasser, Bill Morandi
The advent of transfer hydrogenation and borrowing hydrogen reactions paved the way to manipulate simple alcohols in previously unthinkable manners and circumvent the need for hydrogen gas. Analogously, transfer hydrocarbylation could greatly increase the versatility of tertiary alcohols. However, this reaction remains unexplored because of the challenges associated with the catalytic cleavage of unactivated C–C bonds. Herein, we report a rhodium(I)-catalyzed shuttle arylation cleaving the C(sp2)–C(sp3) bond in unstrained triaryl alcohols via a redox-neutral β-carbon elimination mechanism. A selective transfer hydrocarbylation of substituted (hetero)aryl groups from tertiary alcohols to ketones was realized, employing benign alcohols as latent C-nucleophiles. All preliminary mechanistic experiments support a reversible β-carbon elimination/migratory insertion mechanism. In a broader context, this novel reactivity offers a new platform for the manipulation of tertiary alcohols in catalysis.


European Research Council (ERC Grant 757608 ShuttleCat)

ETH Zürich

Swiss National Science Foundation (SNF 184658)


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ETH Zurich



ORCID For Submitting Author


Declaration of Conflict of Interest