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
Substituent Effects on the Equilibria between Cyclopropylcarbinyl, Bicyclobutonium, Homoallyl, and Cyclobutyl Cations DOI
Sean P. Larmore, Pier Alexandre Champagne

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(11), P. 8146 - 8156

Published: May 16, 2024

The cyclopropylcarbinyl (CPC) and bicyclobutonium (BCB) structures of the C

Language: Английский

Citations

4
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
Stereoselective Nucleophilic Halogenation at CF3-Substituted Nonclassical Carbocation DOI

Veronika Myronova,

Dominique Cahard, Ilan Marek

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(17), P. 3657 - 3660

Published: April 24, 2024

CF3-substituted cyclopropyl carbinol derivatives undergo regioselective and diastereoselective nucleophilic halogenation at the quaternary carbon center to provide acyclic products as a single diastereomer. The selectivity of substitution is rationalized by formation nonclassical cyclopropylcarbinyl cation intermediate, reacting most-substituted center. Tertiary alkyl chlorides, bromides, fluorides adjacent stereogenic C–CF3-motif are diastereomerically pure can be obtained in few catalytic steps from commercially available alkynes.

Language: Английский

Citations

1
Substituent effects on the equilibria between cyclopropylcarbinyl, bicyclobutonium, homoallyl, and cyclobutyl cations DOI Creative Commons
Sean P. Larmore, Pier Alexandre Champagne

Published: Dec. 21, 2023

The cyclopropylcarbinyl (CPC) and bicyclobutonium (BCB) structures of the C4H7+ cation have been proposed as intermediates in various synthetic transformations forming cyclopropylcarbinyl, cyclobutyl, or homoallyl products. It has recently recognized that such cations, when generated from chiral electrophiles, are themselves can react with nucleophiles stereospecifically. However, CPC BCB cations equilibrium each other related cyclobutyl (CB) (HA) which stereospecificity is not guaranteed. Currently, effect substitution on composition mixtures containing CPC/BCB/CB/HA understood, precluding prediction control major products cations. Using Density Functional Theory DLPNO-CCSD(T) calculations, we studied electronic steric effects equilibria between mono- polysubstituted Our results indicate electron-donating groups at C1 position favor structures, while BCB/CB favored for C2 HA C3/C4 positions. Electron-withdrawing yield shallower potential energy surfaces where many energetically accessible. Strong Hammett correlations (σ+) observed substituent effects, appear to be additive nature. In addition, more substituents destabilized compared except donating position. This work provides a predictive model given patterns.

Language: Английский

Citations

1
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