Symmetric Anion Mediated Dynamic Kinetic Asymmetric Knoevenagel Reaction for N−C and N−N Atropisomers Synthesis DOI

Hongyu Qu,

Chenyang Huo,

Jimeng Ge

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(39)

Published: July 3, 2024

Abstract A symmetric anion mediated dynamic kinetic asymmetric Knoevenagel reaction was established as a general and efficient method for accessing both N−C N−N atropisomers. The resulting highly enantio‐pure pyridine‐2,6(1 H ,3 )‐diones exhibit diverse structures functional groups. key to excellent regio‐ remote enantiocontrol could be owed the hydrogen bond between enolate triflamide block of organocatalyst. This connected iminium cation by chiral backbone. mechanism investigation via control experiments, correlation analysis, density theory calculations further revealed how stereochemical information transferred from catalyst into axially )‐diones. synthetic applications also demonstrated reaction's potential.

Language: Английский

Controlling Stereoselectivity with Noncovalent Interactions in Chiral Phosphoric Acid Organocatalysis DOI
Isaiah O. Betinol, Yutao Kuang,

Brian P. Mulley

et al.

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: March 18, 2025

Chiral phosphoric acids (CPAs) have emerged as highly effective Brønsted acid catalysts in an expanding range of asymmetric transformations, often through novel multifunctional substrate activation modes. Versatile and broadly appealing, these benefit from modular tunable structures, compatibility with additives. Given the unique types noncovalent interactions (NCIs) that can be established between CPAs various reactants─such hydrogen bonding, aromatic interactions, van der Waals forces─it is unsurprising catalyst systems become a promising approach for accessing diverse chiral product outcomes. This review aims to provide in-depth exploration mechanisms by which impart stereoselectivity, positioning NCIs central feature connects broad spectrum catalytic reactions. Spanning literature 2004 2024, it covers nucleophilic additions, radical atroposelective bond formations, highlighting applicability CPA organocatalysis. Special emphasis placed on structural mechanistic features govern CPA-substrate well tools techniques developed enhance our understanding their behavior. In addition emphasizing details stereocontrolling elements individual reactions, we carefully structured this natural progression specifics broader, class-level perspective. Overall, findings underscore critical role catalysis significant contributions advancing synthesis.

Language: Английский

Citations

1
Dynamic kinetic resolution and dynamic kinetic asymmetric transformation of atropisomeric biaryls DOI
Jie Zhang,

Xuan-Zhu Huo,

Yidan Liu

et al.

Chem Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 101329 - 101329

Published: March 1, 2025

Language: Английский

Citations

1
Development of Configurationally Labile Biaryl Reagents for Atropisomer Synthesis DOI
Changhui Wu, Jin Yang, Xiaoyuan Zhang

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(28)

Published: May 16, 2024

Abstract Axially chiral biaryl scaffolds are important in pharmaceuticals, natural products, and asymmetric synthesis. Atroposelective ring‐opening of configurationally labile reagents via dynamic kinetic transformation provides a valuable approach to access axially atropisomers. This review summarizes seminal contributions recent advancements on this topic based the use different types reagents.

Language: Английский

Citations

6
Lewis Acid‐Base Interactions as a Racemization Strategy for the Atroposelective Synthesis of (Hetero)biaryls via Dynamic Kinetic Resolution DOI Creative Commons
José A. Carmona, Carlos Rodríguez-Franco, Rosario Fernández

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: unknown

Published: July 8, 2024

Abstract Due to their molecular topology, atropisomers serve as highly valuable chiral frameworks for diverse applications across academic research and industry. Despite the availability of numerous established catalytic methods synthesis, there is still a high demand development novel resourceful strategies. In this concept article, we will detail our studies on use transient Lewis acid‐base interactions (LABI) dynamization strategy synthesis (hetero)biaryl by Dynamic Kinetic Resolution (DKR). The formation cyclic transition states, resulting from interaction between an acidic functionality basic counterpart, plays key role in facilitating racemization substantially reducing barrier atropisomerization. scenario, have employed transformations aimed at neutralizing nature acid, ultimately leading configurationally stable enantioenriched compounds. design substrates employment stereoselective strategies based metal biocatalysis resolution detailed. Specific emphasis preparation axially motifs commonly found catalysis or medicinal chemistry also be given.

Language: Английский

Citations

3
Symmetric Anion Mediated Dynamic Kinetic Asymmetric Knoevenagel Reaction for N−C and N−N Atropisomers Synthesis DOI

Hongyu Qu,

Chenyang Huo,

Jimeng Ge

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 21, 2024

A symmetric anion mediated dynamic kinetic asymmetric Knoevenagel reaction was established as a general and efficient method for accessing both N-C N-N atropisomers. The resulting highly enantio-pure pyridine-2,6(1H,3H)-diones exhibit diverse structures functional groups. key to excellent regio- remote enantiocontrol could be owed the hydrogen bond between enolate triflamide block of organocatalyst. This connected iminium cation by chiral backbone. mechanism investigation via control experiments, correlation analysis, density theory calculations further revealed how stereochemical information transferred from catalyst into axially pyridine-2,6(1H,3H)-diones. synthetic applications also demonstrated reaction's potential.

Language: Английский

Citations

3
Atroposelective biocatalysis employing alcohol dehydrogenases DOI
Gonzalo de Gonzalo,

Julia Carrión-González,

Juan M. Coto‐Cid

et al.

Methods in enzymology on CD-ROM/Methods in enzymology, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Language: Английский

Citations

0
Manganese-Catalyzed Asymmetric Hydrogenation for Atroposelective Dynamic Kinetic Resolution of Heterobiaryl Ketone N-Oxides DOI

Yin-Bo Wan,

Xiang‐Ping Hu

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 17633 - 17641

Published: Nov. 15, 2024

An atroposelective dynamic kinetic resolution of configurationally labile heterobiaryl ketone N-oxides via Mn-catalyzed asymmetric hydrogenation has been disclosed. By use a structurally finely tuned chiral ferrocenyl P,N,N-ligand, the proceeds smoothly under mild conditions with simultaneous installation central and axial chirality, giving wide range atropisomeric 1-arylisoquinoline 2-arylpyridine bearing alcohol structure high diastereo- enantioselectivities. The diastereomer product could be readily prepared in stereospecific way complete inversion chirality Mitsunobu reaction. value this central- axial-chiral N-oxide scaffold is preliminarily demonstrated by its successful utility as catalyst allylation benzaldehyde allyltrichlorosilane.

Language: Английский

Citations

2
Symmetric Anion Mediated Dynamic Kinetic Asymmetric Knoevenagel Reaction for N−C and N−N Atropisomers Synthesis DOI

Hongyu Qu,

Chenyang Huo,

Jimeng Ge

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(39)

Published: July 3, 2024

Abstract A symmetric anion mediated dynamic kinetic asymmetric Knoevenagel reaction was established as a general and efficient method for accessing both N−C N−N atropisomers. The resulting highly enantio‐pure pyridine‐2,6(1 H ,3 )‐diones exhibit diverse structures functional groups. key to excellent regio‐ remote enantiocontrol could be owed the hydrogen bond between enolate triflamide block of organocatalyst. This connected iminium cation by chiral backbone. mechanism investigation via control experiments, correlation analysis, density theory calculations further revealed how stereochemical information transferred from catalyst into axially )‐diones. synthetic applications also demonstrated reaction's potential.

Language: Английский

Citations

1