Stereoinvertive SN1 Through Neighboring Group Participation DOI Creative Commons
Rahul Suresh, Noam Orbach, Ilan Marek

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(31)

Published: May 20, 2024

Abstract Neighboring group participation, the assistance of non‐conjugated electrons to a reaction center, is fundamental phenomenon in chemistry. In framework nucleophilic substitution reactions, neighboring participation known cause rate acceleration, first order kinetics (S N 1), and retention configuration. The latter result double inversion: one when displaces leaving group, second nucleophile substitutes group. This powerful control stereoretention has been widely used organic synthesis for more than century. However, may also lead inversion configuration, which often overlooked. Herein, we review this unique mode stereoinversion, dividing relevant reactions into three classes with aim introduce fresh perspective on different modes stereoinversion via as well factors that stereochemical outcome.

Language: Английский

Stereospecific molecular rearrangement via nucleophilic substitution at quaternary stereocentres in acyclic systems DOI

Kaushalendra Patel,

Ilan Marek

Nature Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 19, 2025

Language: Английский

Citations

1
Stereoinvertive SN1 Through Neighboring Group Participation DOI Creative Commons
Rahul Suresh, Noam Orbach, Ilan Marek

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(31)

Published: May 20, 2024

Abstract Neighboring group participation, the assistance of non‐conjugated electrons to a reaction center, is fundamental phenomenon in chemistry. In framework nucleophilic substitution reactions, neighboring participation known cause rate acceleration, first order kinetics (S N 1), and retention configuration. The latter result double inversion: one when displaces leaving group, second nucleophile substitutes group. This powerful control stereoretention has been widely used organic synthesis for more than century. However, may also lead inversion configuration, which often overlooked. Herein, we review this unique mode stereoinversion, dividing relevant reactions into three classes with aim introduce fresh perspective on different modes stereoinversion via as well factors that stereochemical outcome.

Language: Английский

Citations

3
Formally Stereoretentive SN1 Reactions of Homoallylic Tertiary Alcohols Via Nonclassical Carbocation DOI Creative Commons

Kaushalendra Patel,

Leonie Wilczek,

Francesco Calogero

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: May 27, 2025

We present a stereoretentive nucleophilic substitution of homoallylic tertiary alcohols via the formation nonclassical cyclopropyl carbinyl (CPC) carbocation intermediate. This strategy enables creation highly congested centers with preserved stereocontrol, addressing typical challenges instability and reactivity in SN1 mechanisms. The stabilization CPC intermediate is crucial for achieving precise regio- stereoselectivity, significantly enhancing utility SN1-type mechanisms complex molecule synthesis.

Language: Английский

Citations

0
Stereoinvertive SN1 Through Neighboring Group Participation DOI Creative Commons
Rahul Suresh, Noam Orbach, Ilan Marek

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(31)

Published: May 20, 2024

Abstract Neighboring group participation, the assistance of non‐conjugated electrons to a reaction center, is fundamental phenomenon in chemistry. In framework nucleophilic substitution reactions, neighboring participation known cause rate acceleration, first order kinetics (S N 1), and retention configuration. The latter result double inversion: one when displaces leaving group, second nucleophile substitutes group. This powerful control stereoretention has been widely used organic synthesis for more than century. However, may also lead inversion configuration, which often overlooked. Herein, we review this unique mode stereoinversion, dividing relevant reactions into three classes with aim introduce fresh perspective on different modes stereoinversion via as well factors that stereochemical outcome.

Language: Английский

Citations

0