Access to Regiodefined Tetrahydrofuran-3-one-Derived C-2 Silyl Enol Ethers from α-Triisopropylsilyl-α-diazoketones: The TIPS Trick
The generation of cyclic C-2 silyl enol ethers from the corresponding tetrahydrofuran-3-ones remains a challenge to date. This work provides an alternative two-step approach to access a wide range of regiodefined stable tetrahydrofuran-3-one-derived α-triisopropylsilyl (TIPS) enol ethers from TIPS-diazoacetone (25 examples described) and by extension from TIPS-diazoketones with a high <i>cis</i> selectivity (2 examples). The method involves LDA-induced aldol addition, followed by an unprecedented 1,3-(C→O) silyl shift/intramolecular O-H insertion tandem process, catalyzed by [Rh(nbd)Cl]<sub>2</sub> (2 mol %) in refluxing THF.
Authors
- Anne‐Caroline Chany (ORCID: https://orcid.org/0000-0002-1063-6390)
- Sylvain Henrion (ORCID: https://orcid.org/0000-0001-9170-3091)
- Sigrid Gavelle
- Jérôme Lhoste (ORCID: https://orcid.org/0000-0002-4570-6459)
- Charlotte Boullier
- Catherine Gaulon-Nourry
- Gilles Dujardin
Institutions
- Centre National de la Recherche Scientifique (FR)
- Institut des Molécules et Matériaux du Mans (FR)
Publication Details
- Journal
- Organic Letters
- Published
- 2026-03-26
- DOI
- https://doi.org/10.1021/acs.orglett.6c00147
- Primary Topic
- Cyclopropane Reaction Mechanisms
- Type
- article
- Field-Weighted Citation Impact
- 0.00