Formally Stereoretentive SN1 Reactions of Homoallylic Tertiary Alcohols Via Nonclassical Carbocation

Kaushalendra Patel; Leonie Wilczek; Francesco Calogero; Ilan Marek

doi:10.1021/jacs.5c05680

Formally Stereoretentive S_N1 Reactions of Homoallylic Tertiary Alcohols Via Nonclassical Carbocation

Kaushalendra Patel, Leonie Wilczek, Francesco Calogero, Ilan Marek

Chemistry

Technion - Israel Institute of Technology

Research output: Contribution to journal › Article › peer-review

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 S_N1 mechanisms. The stabilization of the CPC intermediate is crucial for achieving precise regio- and stereoselectivity, significantly enhancing the utility of S_N1-type mechanisms in complex molecule synthesis.

Original language	English
Pages (from-to)	19478-19484
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	147
Issue number	23
DOIs	https://doi.org/10.1021/jacs.5c05680
State	Published - 11 Jun 2025

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.5c05680

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title = "Formally Stereoretentive SN1 Reactions of Homoallylic Tertiary Alcohols Via Nonclassical Carbocation",

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.",

author = "Kaushalendra Patel and Leonie Wilczek and Francesco Calogero and Ilan Marek",

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AU - Patel, Kaushalendra

AU - Wilczek, Leonie

AU - Calogero, Francesco

AU - Marek, Ilan

PY - 2025/6/11

Y1 - 2025/6/11

N2 - 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.

AB - 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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DO - 10.1021/jacs.5c05680

M3 - مقالة

SN - 0002-7863

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 23

ER -

Formally Stereoretentive S_N1 Reactions of Homoallylic Tertiary Alcohols Via Nonclassical Carbocation

Abstract

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