Catalytic Atroposelective Construction of Furan‐Based Axially Chiral Scaffolds DOI

Wei Tan,

Xinyue Wu, Feng Shi

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(21)

Published: July 19, 2024

Abstract Axially chiral furan‐based scaffolds have been recognized as a class of important five‐membered heteroaryl atropisomers, and developing catalytic atroposelective reactions for constructing this is highly desirable. However, the construction such rather underdeveloped due to existence great challenges remote ortho ‐substituents weak configurational stability. To overcome these challenges, synthetic chemists recently paid attention research field, number axially constructed via using different strategies. This concept summarized advances in field pointed out remaining which will promote further development emerging field.

Language: Английский

Catalytic Asymmetric Synthesis of Axially Chiral 3,3'‐Bisindoles by Direct Coupling of Indole Rings DOI

Feng‐Tao Sheng,

Shuang Yang, Shufang Wu

et al.

Chinese Journal of Chemistry, Journal Year: 2022, Volume and Issue: 40(18), P. 2151 - 2160

Published: May 31, 2022

Comprehensive Summary A new strategy for the enantioselective synthesis of axially chiral 3,3'‐bisindoles was devised by direct coupling two indole rings. This makes use C3‐umpolung reactivity 2‐indolylmethanols, which enables catalytic asymmetric addition reaction 2‐indolylmethanols with rationally designed 2‐substituted indoles, thus constructing 3,3'‐bisindole scaffolds in overall excellent yields (up to 98%) high enantioselectivities 96 : 4 er). approach not only has overcome challenges five‐five‐membered heterobiaryls, but also represents a application catalysis. More importantly, this class can undergo variety post‐functionalizations give 3,3'‐bisindole‐based organocatalysts, have found their preliminary applications

Language: Английский

Citations

111
Organocatalytic Enantioselective Synthesis of Axially ChiralN,N′‐Bisindoles DOI

Zhi‐Han Chen,

Tian‐Zhen Li,

Ning‐Yi Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(15)

Published: Feb. 7, 2023

This study establishes the first organocatalytic enantioselective synthesis of axially chiral N,N'-bisindoles via phosphoric acid-catalyzed formal (3+2) cycloadditions indole-based enaminones as novel platform molecules with 2,3-diketoesters, where de novo indole-ring formation is involved. Using this new strategy, various were synthesized in good yields and excellent enantioselectivities (up to 87 % yield 96 ee). More importantly, class exhibited some degree cytotoxicity toward cancer cells was derived into phosphine ligands high catalytic activity. provides a strategy for using asymmetric organocatalysis realize applications such scaffolds medicinal chemistry catalysis.

Language: Английский

Citations

90
Atropisomers with Axial and Point Chirality: Synthesis and Applications DOI
Xing‐Feng Bai, Yu‐Ming Cui, Jian Cao

et al.

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(18), P. 2545 - 2561

Published: Sept. 9, 2022

ConspectusEnantiopure atropisomers have become increasingly important in asymmetric synthesis and catalysis, pharmaceutical science, material science since the discovery of inherent features axial chirality originating from rotational restriction. Despite advances made this field to date, it remains highly desirable construct structurally diverse with potentially useful functions. We propose superposition match point as a strategy access complex building blocks for organic because merging atropisomeric backbones one or more extra chiral elements can topologically broaden three-dimensional environments create scaffolds multiple tunable parameters. Over past decade, we successfully implemented strategic design develop series enantiopure utilized synergistic functions these molecules enhance transfer various catalytic transformations.In Account, present several novel superposed developed our laboratory. In studies, was used synthesize both biaryl non-biaryl commercially available sources. Consequently, were demonstrate importance synergetic specific enantioselective reactions. For example, aromatic amide-derived atropisomers, simplified Xing-Phos arrays, broadly employed Ag-catalyzed [3 + 2] cycloaddition by reactions aldiminoesters activated alkenes imines, well being solvating agents discrimination optically active mandelic acid derivatives. Considering powerful potential also explored transition-metal-catalyzed construction backbone (Ar–alkene, Ar–N axis) bearing ligands functional molecules.The studies presented herein are expected stimulate further research efforts on development matching chirality. addition electron stereohindrance effects, synergy between axial/point groups is proven be special function that cannot ignored promoting reactivity chirality-transfer efficiency synthesis. types capable versatile coordination metal catalysts catalysis highlight power synthetically atropisomers.

Language: Английский

Citations

87
Catalytic Asymmetric Synthesis of Atropisomers Bearing Multiple Chiral Elements: An Emerging Field DOI
Hong‐Hao Zhang,

Tian‐Zhen Li,

Si‐Jia Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(3)

Published: Nov. 2, 2023

With the rapid development of asymmetric catalysis, demand for enantioselective synthesis complex and diverse molecules with different chiral elements is increasing. Owing to unique features atropisomerism, catalytic atropisomers has attracted a considerable interest from chemical science community. In particular, introducing additional elements, such as carbon centered chirality, heteroatomic planar helical into provides an opportunity incorporate new properties axially compounds, thus expanding potential applications atropisomers. Thus, it important perform transformations synthesize bearing multiple elements. spite challenges in transformations, recent years, chemists have devised powerful strategies under organocatalysis or metal synthesizing wide range enantioenriched Therefore, become emerging field. This review summarizes progress this field indicates challenges, thereby promoting horizon.

Language: Английский

Citations

77
Design and catalytic atroposelective synthesis of axially chiral isochromenone-indoles DOI
Qing‐Qing Hang, Shufang Wu, Shuang Yang

et al.

Science China Chemistry, Journal Year: 2022, Volume and Issue: 65(10), P. 1929 - 1937

Published: Sept. 13, 2022

Language: Английский

Citations

76
Asymmetric synthesis of N–N axially chiral compounds via organocatalytic atroposelective N-acylation DOI Creative Commons
Wei Lin, Qun Zhao, Yao Li

et al.

Chemical Science, Journal Year: 2021, Volume and Issue: 13(1), P. 141 - 148

Published: Nov. 24, 2021

A highly efficient atroposelective N -acylation reaction of quinazolinone type benzamides with cinnamic anhydrides for the direct catalytic synthesis optically active atropisomeric derivatives was developed.

Language: Английский

Citations

71
Construction of Axially Chiral Arylpyrroles via Atroposelective Diyne Cyclization DOI

Yang‐Bo Chen,

Li‐Gao Liu,

Can‐Ming Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(23)

Published: March 30, 2023

Axially chiral biaryls widely exist in natural products and pharmaceuticals are used as ligands catalysts asymmetric synthesis. Compared to the well-established axially 6-membered biaryl skeletons, examples of 5-membered have been quite scarce, mono-substituted 3-arylpyrrole atropisomers not reported. Here, we disclose a copper-catalyzed atroposelective diyne cyclization for construction range arylpyrrole good excellent yields with generally enantioselectivities via oxidation X-H insertion vinyl cations. Importantly, this protocol only represents first synthesis atropisomers, but also constitutes example atropisomer Theoretical calculations further support mechanism cation-involved elucidate origin enantioselectivity.

Language: Английский

Citations

34
Design and Catalytic Asymmetric Synthesis of Furan‐Indole Compounds Bearing both Axial and Central Chirality DOI
Jing‐Yi Wang,

Cong‐Hui Gao,

Cheng Ma

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(8)

Published: Dec. 29, 2023

Abstract In the chemistry community, catalytic asymmetric synthesis of furan‐based compounds bearing both axial and central chirality has proven to be a significant but challenging issue owing importance difficulty in constructing such frameworks. this work, we have realized first five‐five‐membered via organocatalytic (2+4) annulation achiral furan‐indoles with 2,3‐indolyldimethanols uncommon regioselectivity. By strategy, furan‐indole were synthesized high yields excellent regio‐, diastereo‐, enantioselectivities. Moreover, theoretical calculations conducted provide an in‐depth understanding reaction pathway, activation mode, origin selectivity.

Language: Английский

Citations

32
Recent advances in the construction of axially chiral arylpyrroles DOI

Yang‐Bo Chen,

Ye-Nan Yang,

Xuan-Zhu Huo

et al.

Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(9), P. 2480 - 2491

Published: Aug. 9, 2023

Language: Английский

Citations

30
Dynamic Kinetic Resolution of Indole-Based Sulfenylated Heterobiaryls by Rhodium-Catalyzed Atroposelective Reductive Aldol Reaction DOI Creative Commons
Carlos Rodríguez-Franco, Abel Ros, Pedro Merino

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(18), P. 12134 - 12141

Published: Aug. 30, 2023

A highly enantio- and diastereoselective dynamic kinetic resolution (DKR) of configurationally labile 3-aryl indole-2-carbaldehydes is described. The DKR proceeds via a Rh-catalyzed intermolecular asymmetric reductive aldol reaction with acrylate esters, simultaneous generation three stereogenic elements. strategy relies on the labilization axis that takes place thanks to transient Lewis acid-base interaction (LABI) between formyl group thioether moiety strategically located at ortho' position. atropisomeric indole products present high degree functionalization can be further converted series axially chiral derivatives, thereby expanding their potential application in drug discovery catalysis.

Language: Английский

Citations

30