Formally Stereoretentive S<sub>N</sub>1 Reactions of Homoallylic Tertiary Alcohols Via Nonclassical Carbocation
We present a stereoretentive nucleophilic substitution of homoallylic tertiary alcohols via the formation of a nonclassical cyclopropyl carbinyl (CPC) carbocation intermediate. This strategy enables the creation of highly congested tertiary centers with preserved stereocontrol, addressing the typical challenges of carbocation instability and reactivity in S<sub>N</sub>1 mechanisms. The stabilization of the CPC intermediate is crucial for achieving precise regio- and stereoselectivity, significantly enhancing the utility of S<sub>N</sub>1-type mechanisms in complex molecule synthesis.
Authors
- Kaushalendra Patel (ORCID: https://orcid.org/0009-0002-9083-4131)
- Francesco Calogero (ORCID: https://orcid.org/0000-0002-8609-5148)
- Ilan Marek (ORCID: https://orcid.org/0000-0001-9154-2320)
- Leonie Wilczek
Institutions
- Technion – Israel Institute of Technology (IL)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2025-05-27
- DOI
- https://doi.org/10.1021/jacs.5c05680
- Citations
- 3
- Primary Topic
- Molecular Spectroscopy and Structure
- Type
- article
- Field-Weighted Citation Impact
- 2.27
Funders
- Israel Science Foundation