Recent Advances on Catalytic Atroposelective Synthesis of Planar‐Chiral Macrocycles DOI
Gongming Yang, Jian Wang

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(42)

Published: Aug. 6, 2024

Abstract Planar‐chiral skeletons widely exist in natural products, bioactive compounds, and other functional molecules. Although significant progress has been made the field of asymmetric synthesis centrally or axially chiral molecules over past years, enantioselective constructing planar chirality is still a big obstacle numerous efforts have this field. Previous works mainly focused on assembly planar‐chiral [2,2]‐paracyclophanes metallocenes. This Minireview describes recent advancements catalytic macrocycles, including ansa chain construction, plane formation transformation strategies. It anticipated that will sever as source inspiration for developing new unconventional procedures access to skeletons.

Language: Английский

N-Heterocyclic Carbene-Catalyzed Highly Enantioselective Macrolactonization to Access Planar-Chiral Macrocycles DOI

Jiaming Wang,

Meng Wang,

Yilu Wen

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(5), P. 1040 - 1045

Published: Jan. 31, 2024

An N-heterocyclic carbene (NHC)-catalyzed atroposelective macrolactonization has been disclosed. This approach affords planar-chiral macrocycles in high yields with excellent enantioselectivities over a broad substrate scope. Controlled experiments suggest that the enantioselectivity might arise from cation–n interaction between acyl azolium and electron-rich moiety substrate. mechanism is supported by density functional theory calculations, which also an important π–π stabilizing transition state.

Language: Английский

Citations

12
Rhodium(III)-Catalyzed Atroposelective Indolization to Access Planar-Chiral Macrocycles DOI

Hongxuan Zhai,

Kang Lv, Jiayan Li

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(42), P. 29214 - 29223

Published: Oct. 9, 2024

Macrocycles incorporating conformationally defined indoles are widely found in bioactive natural products. However, the catalytic enantioselective synthesis of planar-chiral via indolization involving macrocyclization remains elusive. Herein, we present first rhodium(III)-catalyzed atroposelective macrocyclization, which involves C-H activation aniline, and a subsequent oxidation [3 + 2] annulation reaction with an intramolecular alkyne. This protocol achieves construction indoles, planar chirality control single step. Importantly, this strategy produces macrocyclic atropisomers bearing full-carbon ansa chains, represent challenging targets organic synthesis. Thermodynamic experiments revealed that rotational barrier chain-linked atropisomer was lower than oxa-ansa chain. The mechanism elucidated by computational studies, alkyne insertion steps collectively determined enantioselectivity.

Language: Английский

Citations

8
Recent Advances on Catalytic Atroposelective Synthesis of Planar‐Chiral Macrocycles DOI
Gongming Yang, Jian Wang

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

Published: Aug. 6, 2024

Planar-chiral skeletons widely exist in natural products, bioactive compounds, and other functional molecules. Although significant progress has been made the field of asymmetric synthesis centrally or axially chiral molecules over past years, enantioselective constructing planar chirality is still a big obstacle numerous efforts have this field. Previous works mainly focused on assembly planar-chiral [2,2]-paracyclophanes metallocenes. This Minireview describes recent advancements catalytic macrocycles, including ansa chain construction, plane formation transformation strategies. It anticipated that will sever as source inspiration for developing new unconventional procedures access to skeletons.

Language: Английский

Citations

5
Pd/NHC sequentially catalyzed atroposelective synthesis of planar-chiral macrocycles DOI Creative Commons
Gongming Yang,

Shangde Liu,

Shun‐Jun Ji

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Planar-chiral macrocycles play a pivotal role in host-guest chemistry and drug discovery. However, compared with the synthesis of other types chiral compounds, asymmetric construction planar-chiral still remains forbidding challenge. Herein, we report sequential palladium N-heterocyclic carbene catalysis to build macrocycles. This protocol features broad scope good functional group tolerance, allows rapid assembling excellent enantioselectivities.

Language: Английский

Citations

5
Catalytic Enantioselective Macrocyclization for the Synthesis of Planar‐Chiral Cyclophanes: Recent Updates DOI
Ziyang Dong, Jia Li, Changgui Zhao

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(47)

Published: Aug. 28, 2024

Abstract The planar chirality of macrocycles is a fascinating research topic. Locking the configurational flip between benzene ring and macrocycle leads to chirality, which can significantly enhance biological activity cyclophanes. Planar‐chiral cyclophanes are widely used in pharmaceuticals, chiral catalysts, functional materials. However, accessing planar‐chiral via asymmetric catalysis has remained challenging. Among various strategies, macrocyclization provides powerful tool for This method allows control when constructing greatly improves efficiency. There three types reactions: transition metal‐catalyzed, organocatalyzed, biocatalyzed. In addition, confinement strategy breaks through conservative synthetic approaches. review summarizes these achievements, aiming highlight catalytic synthesis inspire interested researchers.

Language: Английский

Citations

4
An Approach for Highly Enantioselective Synthesis of meta-Disubstituted [n]Paracyclophanes DOI
Jia Li, Ziyang Dong,

Hongxuan Zhai

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 27, 2024

Atroposelective synthesis of

Language: Английский

Citations

4
Enantioselective synthesis of inherently chiral sulfur-containing calix[4]arenes via chiral sulfide catalyzed desymmetrizing aromatic sulfenylation DOI Creative Commons
Xinyu Zhang,

Deng Zhu,

Ren‐Fei Cao

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Nov. 15, 2024

Inherently chiral calixarenes hold great potential for applications in recognition, sensing, and asymmetric catalysis due to their unique structures. However, special structures relatively large sizes, the catalytic synthesis of inherently is challenging with very limited examples available. Here, we present an efficient method enantioselective sulfur-containing calix[4]arenes through desymmetrizing electrophilic sulfenylation calix[4]arenes. This reaction enabled by a 1,1'-binaphthyl-2,2'-diamine-derived sulfide catalyst hexafluoroisopropanol. Various are obtained moderate excellent yields high enantioselectivities. Control experiments indicate that thermodynamically favored C-SAr product formed from kinetically N-SAr combination hexafluoroisopropanol crucially important both enantioselectivity reactivity. Due authors report

Language: Английский

Citations

4
Conformationally Defined Planar-Chiral [n]Paracyclophanes Stabilized by Chiral Ansa Chains DOI Creative Commons
Changgui Zhao, Jiaming Wang,

Yilu Wen

et al.

Research Square (Research Square), Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 6, 2025

Abstract Although chiral substituents have been incorporated into ansa chains to stabilize the conformations of cyclophanes and modulate the biological activities pharmaceuticals, asymmetric syntheses these atropisomers relies on substrate-induced diastereoselective macrocyclization. Consequently, enantio-, atrop-, macrocyclizations are yet be reported. Herein, we describe a N-heterocyclic carbene (NHC) phosphoric acid (CPA) dual-catalytic process for desymmetrization 1,3-diols, achieve macrocyclization stereoselective control over two elements. It was deduced that hydrogen bonding CPA with 1,3-diols enhanced diastereoselectivity process. As result, various planar-chiral bearing were synthesized. Thermodynamic experiments revealed presence an all-carbon quaternary carbon center chain significantly increased rotational barriers cyclophanes. Moreover, density functional theory calculations suggested substituent shrinks by compressing bond angle, thereby rendering conformational rotation reaction more challenging.

Language: Английский

Citations

0
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
Enantioselective Synthesis of Inherently Chiral Pillar[5]Arenes Through Copper‐Catalyzed Azide–Alkyne Cycloaddition DOI Open Access
Wenguang Zhou, Longlong Xi,

Meiru Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

Pillar[n]arenes have been extensively investigated as carrier materials for applications in host-guest chemistry, nanoscience, information science, and other domains. Despite its success, the enantioselective synthesis of pillar[n]arenes is challenging has not yet achieved. Herein, we present a novel asymmetric extended side-arm strategy synthesizing chiral pillar[5]arenes through an iterative copper-catalyzed azide-alkyne cycloaddition reaction. An increase steric hindrance on both sides macrocyclic molecule efficiently produced wide range high yields with excellent enantioselectivities. Moreover, this principle enables to enantioselectively functionalized different triazoles using one-pot process.

Language: Английский

Citations

0