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Formally Stereoretentive SN1 Reactions of Homoallylic Tertiary Alcohols Via Nonclassical Carbocation
Kaushalendra Patel1, Leonie Wilczek1, Francesco Calogero1
1Schulich Faculty of Chemistry and the Resnick Sustainability Center for Catalysis, Technion-Israel Institute of Technology, Haifa, 3200009, Israel.
Abstract:
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 SN1 mechanisms. The stabilization of the CPC intermediate is crucial for achieving precise regio- and stereoselectivity, significantly enhancing the utility of SN1-type mechanisms in complex molecule synthesis.
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