Catalytic Synthesis of Atropoisomers via Non‐Canonical Friedel‐Crafts Reactions DOI

Xutong Ye,

Xixiang Yu,

Rui Deng

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(8), P. 1670 - 1706

Published: Feb. 29, 2024

Abstract The Friedel‐Crafts reaction stands as a powerful synthetic tool for C−H functionalization of aromatic feedstocks, which is conventionally realized through electrophilic alkylation and acylation. burgeoning interests in axially chiral compounds across diverse fields have spurred extensive exploration this classic transformation catalytic atroposelective synthesis. Consequently, the past decade has witnessed rapid expansion various non‐canonical reactions, including arylation, alkenylation, halogenation, sulfenylation, amination aryl bonds, thereby delving into new chemical spaces. A range methods been devised these significant arene functionalization. This review provides comprehensive overview cutting‐edge synthesis atropoisomers categorized three parts based on type bond formation aromatics: C( sp 2 )−C( 3 ) formations, formations )−heteroatom formations. richness electrophiles modulation atroposelectivity by organocatalysts, particularly Brønsted acids, are elucidated. We anticipate that repertoire asymmetric will continue to flourish be demonstrated not only scientific researches but also industrial organic

Language: Английский

Enantioselective Synthesis of Planar‐Chiral Sulfur‐Containing Cyclophanes by Chiral Sulfide Catalyzed Electrophilic Sulfenylation of Arenes DOI

Deng Zhu,

Tong Mu,

Ze‐Long Li

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(10)

Published: Jan. 17, 2024

Abstract An efficient catalytic asymmetric electrophilic sulfenylation reaction for the synthesis of planar‐chiral sulfur‐containing cyclophanes has been developed first time. This was achieved by using a new Lewis base catalyst and ortho ‐trifluoromethyl‐substituted sulfenylating reagent. Using substrates with low rotational energy barrier, transformation proceeded through dynamic kinetic resolution, high barrier allowed to undergo resolution process. Meanwhile, this compatible desymmetrization process when symmetric were used. Various readily obtained in moderate excellent yields enantioselectivities (up 97 % yield 95 ee). approach used synthesize pharmaceutically relevant molecules. Density functional theory calculations showed that π‐π interactions between sulfenyl group aromatic ring substrate play crucial role enantioinduction reaction.

Language: Английский

Citations

18
Developing Biarylhemiboronic Esters for Biaryl Atropisomer Synthesis via Dynamic Kinetic Atroposelective Suzuki–Miyaura Cross-Coupling DOI

Yiming Yang,

Changhui Wu,

Junhao Xing

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(9), P. 6283 - 6293

Published: Feb. 21, 2024

We herein introduce biarylhemiboronic esters as a new type of bridged biaryl reagent for asymmetric synthesis axially chiral structures, and the palladium-catalyzed Suzuki-Miyaura cross-coupling is developed. This dynamic kinetic atroposelective coupling reaction exhibits high enantioselectivity, good functional group tolerance, broad substrate scope. The synthetic application current method was demonstrated by transformations product programmed polyarene. Preliminary mechanistic studies suggested that proceeded via an enantio-determining transmetalation step.

Language: Английский

Citations

16
Dynamic Kinetic Reductive Grignard-Type Addition for the Construction of Axial and Central Chirality DOI

Ya-Ping Shao,

Yong‐Min Liang

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 1147 - 1157

Published: Jan. 3, 2025

This study describes a photoredox/cobalt dual-catalyzed asymmetric Grignard-type addition reaction, enabling the synthesis of axially chiral hexatomic (six–six) N-heterobiaryls bearing extra secondary alcohol unit via an efficient dynamic kinetic transformation racemic N-heterobiaryl triflate substrates. The conversion facilitated both photoredox and classical reductive reaction conditions exhibits good functional group tolerance, broad substrate scope, satisfactory stereoselectivity. Furthermore, control experiments density theory calculations provide preliminary mechanistic insights.

Language: Английский

Citations

3
Atroposelective Diverse Remote meta-C–H Functionalization via Kinetic Resolution DOI
Jianjun Li, Xiaoming Zeng, Xin Kuang

et al.

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

Published: Feb. 14, 2025

A diverse range of Pd(II)-catalyzed enantioselective C-H activation reactions have been developed to construct point, axial, and planar chirality. Despite the importance chiral biaryl scaffolds in bioactive molecules ligands, atroposelective functionalization at meta-position remains a significant challenge. Here, we realized rare remote meta-C-H with monoprotected amino acid (MPAA) ligand racemic transient norbornene mediator. The reaction starts ortho-C-H via kinetic resolution give biaryl-palladium intermediate, which subsequently undergoes Catellani relay afford meta-functionalized products (S-factors up 458). obtained enantioenriched quinoline-based atropisomers are ubiquitous natural products, pharmaceuticals, functional materials. Moreover, unprecedented meta-alkenylation alkynylation also using this approach. wide synthetic applications 8-aryl quinolines, including synthesis novel P,N-ligand materials CPL activity, demonstrated.

Language: Английский

Citations

2
Atropisomeric Carboxylic Acids Synthesis via Nickel‐Catalyzed Enantioconvergent Carboxylation of Aza‐Biaryl Triflates with CO2 DOI
Xiao‐Wang Chen, Chao Li, Yong‐Yuan Gui

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(22)

Published: March 26, 2024

Abstract Upgrading CO 2 to value‐added chiral molecules via catalytic asymmetric C−C bond formation is a highly important yet challenging task. Although great progress on the of centrally carboxylic acids has been achieved, construction axially with never reported date. Herein, we report first synthesis , which enabled by nickel‐catalyzed dynamic kinetic reductive carboxylation racemic aza‐biaryl triflates. A variety acids, are valuable but difficult obtain catalysis, generated in an enantioconvergent version. This new methodology features good functional group tolerance, easy scale‐up, facile transformation and avoids cumbersome steps, handling organometallic reagents using stoichiometric materials. Mechanistic investigations indicate process induced nickel catalysis.

Language: Английский

Citations

14
Organocatalytic Atroposelective Dynamic Kinetic Resolution Involving Ring Manipulations DOI

Qin Shi,

Fang Fang, Dao‐Juan Cheng

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(6), P. 1269 - 1284

Published: Jan. 31, 2024

Abstract Axially chiral architectures exist widely in natural products, biologically relevant molecules, ligands and catalysts as well functional materials. Therefore, catalytic asymmetric synthesis of atropisomers has become one the most fast‐growing fields community chemistry rapid advances have occurred. Among different methods reported, organocatalytic atroposelective dynamic kinetic resolution (DKR) involving ring manipulations stands out a cutting‐edge technology to construct axial chirality from point atom/step economy. In this DKR strategy, configurational lability starting materials originates chirally‐labile structure cyclic substrates/intermediates or transient formation through noncovalent interactions acyclic substrates. The two material are equilibrium reaction medium, ensuring constant transformation less reactive atropisomer into more one, then single enantiopure product presence an appropriate organocatalyst. This review summarizes recent advancements on topic, including their scopes, limitations, mechanisms, applications provides some insights further developments.

Language: Английский

Citations

11
Dual Catalytic C(sp2)–H Activation of Azaheterocycles toward C–N Atropisomers DOI
Juntao Sun, Yiyao Hu, Wen‐Ji He

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 3700 - 3710

Published: Feb. 14, 2025

Language: Английский

Citations

1
Organocatalytic Atroposelective Hydroselenation of Alkynes To Access Axially Chiral Vinyl Selenides DOI

Yi-Xin Wang,

Jing-Run Wang,

Chen Cui

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4051 - 4060

Published: Feb. 20, 2025

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