Recent advances toward the catalytic enantioselective synthesis of planar chiral cyclophanes DOI
Kai Zhu, Lei Yang, Yang Yang

et al.

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: 36(7), P. 110678 - 110678

Published: Nov. 26, 2024

Language: Английский

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
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

6
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
Asymmetric construction of axial and planar chirality with N-heterocyclic carbene (NHC) organocatalysis DOI
Meng Zhang,

Xiaoqun Yang,

Xiaolin Peng

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 30, 2024

Language: Английский

Citations

5
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
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
N-Heterocyclic carbene-catalyzed enantioselective (dynamic) kinetic resolution for the assembly of inherently chiral macrocycles DOI Creative Commons
Zhipeng Li,

Jingyang Zhang,

Wanmeng Zhu

et al.

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

Published: Jan. 1, 2025

We have successfully achieved the highly enantioselective synthesis of inherently chiral macrocycles through NHC-catalyzed asymmetric esterification heterocalixaromatics.

Language: Английский

Citations

0
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
Enantioselective Synthesis of Planar/Multiple Chiral [n]Cyclophanes through Asymmetric Allylation DOI Open Access
Ziyang Wang, Xinxin Zhang,

Yidan Sun

et al.

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: 43(11), P. 1263 - 1270

Published: March 7, 2025

Comprehensive Summary Planar‐chiral cyclophanes with carbon‐centered chirality are important targets in natural products and pharmaceuticals. However, synthesizing such planar chiral two stereogenic elements via a one‐step asymmetric reaction remains formidable challenge. Herein, we present an efficient kinetic resolution method for planar‐chiral [ n ]cyclophanes chirality. This is achieved through the enantioselective allylation of racemic aldehyde catalyzed by Bi(OAc) 3 phosphoric acid. The delivers multiple high yields excellent enantioselectivities, showcasing remarkable efficiency ( s factor up to 292). broad substrate scope, scalability, potential derivatization highlight value this methodology. DFT calculations have also been performed provide insights into origin experimentally observed diastereo‐ enantioselectivity reaction.

Language: Английский

Citations

0
Enantio-, atrop-, and diastereoselective macrolactonization to access type III cyclophanes DOI Creative Commons
Jiaming Wang, Kang Lv,

Yilu Wen

et al.

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

Published: April 3, 2025

Language: Английский

Citations

0