Peroxy-Carbenium Mediated Asymmetric Synthesis of 1,2-Dioxanes and 1,2-Dioxolanes DOI
Laurent Ferrié, Bruno Figadère, Nicolas Jamey

et al.

Published: Sept. 24, 2024

The endoperoxide scaffold is found in numerous natural products and synthetic substances with pharmaceutical interest. principal challenge to their access remains the preparation of chiral compounds, due weakness peroxide bond, which limits scope available or applicable methods. Here, we demonstrate how peroxycarbenium species can be trapped by silylated nucleophiles high enantioselectivities, diastereoselectivities when applicable, using a imidophosphorimidate (IDPi) as catalyst. methodology broad, encompassing large varie-ty enoxysilanes, yielding 1,2-dioxanes 1,2-dioxolanes. Peroxides converted into alcohols trans-epoxides, was applied key step total synthesis ethyl plakortide Z, demonstrated enhanced selectivity. Kinetic studies that tert-butyldimethylsilylated are more potent than trime-thylsilylated ones. Furthermore, it observed reaction necessitates an induction period, indicating formation silylium behaves true

Language: Английский

Peroxycarbenium-Mediated Asymmetric Synthesis of 1,2-Dioxanes and 1,2-Dioxolanes DOI

Bastien Champciaux,

Nicolas Jamey, Bruno Figadère

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: 147(4), P. 3353 - 3359

Published: Jan. 17, 2025

The endoperoxide scaffold is found in numerous natural products and synthetic substances of pharmaceutical interest. main challenge to their access remains the preparation chiral compounds due weakness peroxide bond, which limits scope available or applicable methods. Here, we demonstrate how peroxycarbenium species can be trapped by silylated nucleophiles with high enantioselectivities diastereoselectivities when applicable, using a imidophosphorimidate (IDPi) as catalyst. methodology broad, encompassing large variety enoxysilanes yielding 1,2-dioxanes 1,2-dioxolanes. Peroxides converted into alcohols trans-epoxides, was applied key step total synthesis ethyl plakortide Z, enhancing selectivity compared conventional Lewis acid-catalyzed transformation. Kinetic studies have shown that reaction necessitates an induction period, indicating formation silylium behaves true

Language: Английский

Citations

1
Chiral sulfide and achiral sulfonic acid cocatalyzed enantioselective electrophilic tandem selenylation semipinacol rearrangement of allenols DOI Creative Commons

Ren‐Fei Cao,

Ruirui Su,

Zhiwei Wei

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: March 3, 2025

A highly enantioselective electrophilic selenylation/semipinacol rearrangement of allenols has been developed, which is enabled by the cooperative catalysis a chiral sulfide and an achiral sulfonic acid. The designed synthesized catalyst selenylating reagent play crucial role in enhancing both enantioselectivity reactivity. This approach exhibits excellent regio-, chemo-, enantioselectivity, providing access to diverse enantioenriched cyclopentanones featuring arylselenovinyl-substituted quaternary carbon stereocenter. Furthermore, these products can be transformed into synthetically valuable alkyne, vinyl bromide, aniline derivatives. Mechanistic studies reveal that combination acid not only facilitates formation catalytically active species, but also governs reaction. Meanwhile, density functional theory calculations disclose four hydrogen bond interactions π‧‧‧π interaction are responsible for observed enantioselectivity. Rearrangement reactions serve as steps syntheses biologically provide intellectual conceptual curiosities within broad field organic chemistry. Here, authors report allenols, catalysed Lewis base.

Language: Английский

Citations

0
Bis-indole chiral architectures for asymmetric catalysis DOI Creative Commons
Junshan Lai, Benjamin List, Jolene P. Reid

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: April 17, 2025

Abstract Chiral scaffolds are essential to the advancement of asymmetric synthesis, yet development privileged motifs that more effectively communicate asymmetry constitutes a grand challenge for chemists. Here we describe method using confined chiral Brønsted acid catalyst combine two inexpensive and widely available materials—indole acetone—into class C₂-symmetric, spirocyclic compounds called SPINDOLE. SPINDOLEs extend versatility established frameworks by offering greater flexibility ease synthesis. The resulting can be readily modified create diverse structures excel in promoting highly selective reactions such as hydrogenation, allylic alkylation, hydroboration, Michael addition. This work introduces powerful strategy advancing catalysis, enabling creation versatile with broad synthetic potential.

Language: Английский

Citations

0
Relative Generality and Risk: Quantitative Measures for Broad Catalyst Success DOI

Michal Sanocki,

H Russell, Jasemine Handjaya

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(22), P. 16849 - 16860

Published: Oct. 31, 2024

The performance of chiral catalysts is typically evaluated against empirical reaction outputs like yield and selectivity with traditional analyses limited to a single model system. Expansion the space permits be assessed for generality, this provides another useful metric measuring effectiveness catalyst. catalyst generality algorithm will assign quantitative values structures, but such broad assessments are applied assumption that reactions under evaluation more or less same by disregarding any inherent challenges associated particular class. To address limitation, we introduce two metrics: relative risk. These designed correct variations in difficulty enable nuanced specific demands each reaction. We show number challenging examples these metrics allow researchers distinguish between genuinely exhibiting superior those appearing favorable due application toward demanding reactions. This represents significant advancement quantifying success demonstrated applications retrospective early insights into emerging classes.

Language: Английский

Citations

3
Catalytic Asymmetric Reactions of Ketimines and Alkenes via [2 + 2] Cycloaddition: Chemical Reactivity Controlled by Switching a Heteroatom DOI
Qun Zhao, Yao Li, Zhiyuan Ren

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(46), P. 32088 - 32097

Published: Nov. 8, 2024

Azetidine units are commonly found in natural products and biologically active drugs. The [2 + 2] cycloaddition of imines alkenes has been extensively used the synthesis such structures, while enantioselective approaches remain elusive. Herein, an efficient B(C

Language: Английский

Citations

1
Peroxy-Carbenium Mediated Asymmetric Synthesis of 1,2-Dioxanes and 1,2-Dioxolanes DOI
Laurent Ferrié, Bruno Figadère, Nicolas Jamey

et al.

Published: Sept. 24, 2024

The endoperoxide scaffold is found in numerous natural products and synthetic substances with pharmaceutical interest. principal challenge to their access remains the preparation of chiral compounds, due weakness peroxide bond, which limits scope available or applicable methods. Here, we demonstrate how peroxycarbenium species can be trapped by silylated nucleophiles high enantioselectivities, diastereoselectivities when applicable, using a imidophosphorimidate (IDPi) as catalyst. methodology broad, encompassing large varie-ty enoxysilanes, yielding 1,2-dioxanes 1,2-dioxolanes. Peroxides converted into alcohols trans-epoxides, was applied key step total synthesis ethyl plakortide Z, demonstrated enhanced selectivity. Kinetic studies that tert-butyldimethylsilylated are more potent than trime-thylsilylated ones. Furthermore, it observed reaction necessitates an induction period, indicating formation silylium behaves true

Language: Английский

Citations

0