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, Journal Year: 2023, Volume and Issue: 136(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

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
A Dynamic Kinetic Resolution Approach to Axially Chiral Diaryl Ethers by Catalytic Atroposelective Transfer Hydrogenation DOI

Linlong Dai,

Yuheng Liu, Qing Xu

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(7)

Published: Dec. 20, 2022

Diaryl ethers are widespread in biologically active compounds, ligands and catalysts. It is known that the diaryl ether skeleton may exhibit atropisomerism when both aryl rings unsymmetrically substituted with bulky groups. Despite recent advances, only very few catalytic asymmetric methods have been developed to construct such axially chiral compounds. We describe herein a dynamic kinetic resolution approach via Brønsted acid catalyzed atroposelective transfer hydrogenation (ATH) reaction of dicarbaldehydes anilines. The desired could be obtained moderate good chemical yields (up 79 %) high enantioselectivities 95 % ee) under standard conditions. Such structural motifs interesting precursors for further transformations potential applications synthesis or

Language: Английский

Citations

49
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
Atroposelective Electrophilic Sulfenylation ofN‐Aryl Aminoquinone Derivatives Catalyzed by Chiral SPINOL‐Derived Sulfide DOI

Deng Zhu,

Yu Lu, Huiyun Luo

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(42)

Published: Aug. 30, 2022

Atroposelective electrophilic sulfenylation of N-aryl aminoquinone derivatives has been achieved for the first time. This transformation is enabled by a new chiral 6,6'-disubstituted SPINOL-derived sulfide catalyst, which was synthesized and then successfully explored catalyzing enantioselective reactions. Various axially sulfur-containing diarylamine were readily obtained in moderate to excellent yields with enantioselectivities. A class relatively flexible stereogenic C-N axes easily constructed. The experimental results computational study suggested that an intramolecular N-H⋅⋅⋅S hydrogen bond important stability axis, consistent our hypothesis. Density functional theory calculations revealed origin atroposelectivity underscored importance catalyst rigidity this reaction.

Language: Английский

Citations

35
Silver-Catalyzed Direct Nucleophilic Cyclization: Enantioselective De Novo Synthesis of C–C Axially Chiral 2-Arylindoles DOI

Liangbin Yu,

Junjun Liu,

Shiyu Xiang

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(3), P. 522 - 527

Published: Jan. 18, 2023

Atropisomeric indoles widely exist in natural products, pharmaceuticals, functional materials, and catalysts for their featured biological activities, photoelectric properties, catalytic while facile de novo construction of this motif remains underexplored. Herein, we report a chiral silver phosphate-catalyzed direct 5-endo-dig nucleophilic cyclization 2-alkynylanilins under mild conditions, affording various C-C axially 2-arylindoles high to excellent yields enantioselectivities. Control experiments implied the cooperative catalysis AgOAc phosphoric acid, wherein former accelerated desired transformation latter improved enantioselectivity. In addition, as first example silver-catalyzed enantioselective synthesis indole skeletons, synthetic applications products' thermal stability have been investigated.

Language: Английский

Citations

22
Organocatalytic Nazarov-type cyclization of 3-alkynyl-2-indolylmethanols: construction of axially chiral cyclopenta[b]indole scaffolds DOI Open Access
Ping Wu, Xinyu Yan,

Song Jiang

et al.

Chemical Synthesis, Journal Year: 2023, Volume and Issue: 3(1), P. 6 - 6

Published: Jan. 1, 2023

In recent years, it has become an urgent task to design new types of indole-based platform molecules for Nazarov-type cyclizations and develop organocatalytic synthesizing indole derivatives. To fulfill this task, in work, by changing the alkynyl terminal substituent from t-Bu aryl group, reactivity 3-alkynyl-2-indolylmethanols is modulated serve as competent substrates Brønsted acid-catalyzed cyclization. Based on reactivity, first cyclization aryl-substituted with 2-naphthols accomplished, leading efficient construction a class axially chiral 3, 4-dihydrocyclopenta[b]indole scaffolds. This preliminary investigation asymmetric provides optional strategy atroposelective cyclopenta[b]indole addition, preparation optical purity established through resolution, which could complementary method catalytic approaches.

Language: Английский

Citations

20
Enantioselective Synthesis of Heteroatom‐Linked Non‐Biaryl Atropisomers DOI Creative Commons

Abdelati Naghim,

Jean Rodriguez, Olivier Chuzel

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(30)

Published: May 15, 2024

Atropisomers hold significant fascination, not only for their prevalence in natural compounds but also biological importance and wide-ranging applications as chiral materials, ligands, organocatalysts. While biaryl heterobiaryl atropisomers are commonly studied, the enantioselective synthesis of less abundant heteroatom-linked non-biaryl presents a formidable challenge modern organic synthesis. Unlike classical atropisomers, these molecules allow rotation around two bonds, resulting low barriers to enantiomerization through concerted bond rotations. In recent years discovery new configurationally stable rare scaffolds such aryl amines, ethers sulfones well innovative methodologies control configuration have been disclosed literature constitute topic this minireview.

Language: Английский

Citations

7
Organocatalytic enantioselective synthesis of Csp2–N atropisomers via formal Csp2–O bond amination DOI Creative Commons

Chenxiao Qian,

Jing Huang, Tingting Huang

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(11), P. 3893 - 3900

Published: Jan. 1, 2024

An organocatalyzed asymmetric synthesis of C sp2 –N atropisomers by formal –O amination has been established from 3-alkynyl-3-hydroxyisoindolinones and 1-methylnaphthalen-2-ols.

Language: Английский

Citations

5
Enantioselective Aminative Dearomatization of Indoles via Electrophilic 1,6-Addition of p-Quinone Diimides (p-QDIs) DOI

Parbat Subba,

Sushree Ranjan Sahoo,

Chhavi Khajuria

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(23), P. 4932 - 4937

Published: June 3, 2024

Herein we report the first use of p-quinone diimide for aminative dearomatization 2,3-disubstituted indoles to furnish C3 aza-quaternary chiral indolenines. This approach, which proceeds via an electrophilic 1,6-addition diimide, allows synthesis array optically active indolenines with high yields and excellent enantioselectivities. A one-pot approach same has also been established further improve synthetic accessibility this protocol.

Language: Английский

Citations

5
Atroposelective Synthesis of 2‐Arylindoles via Chiral Phosphoric Acid‐Catalyzed Direct Amination of Indoles† DOI
Wen Bao, Ye‐Hui Chen, Yuwei Liu

et al.

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 42(7), P. 731 - 735

Published: Nov. 29, 2023

Comprehensive Summary Indole‐based atropisomers are a very important class of axially chiral compounds. However, the atroposelective synthesis 2‐arylindole remains largely unexplored. In this study, we report successful atropisomeric 2‐arylindoles using direct amination indoles with p ‐quinonediimines in presence phosphoric acid as catalyst. Quinonediimine acts an aminating reagent through formal polarity inversion imine. The malonate group on 2‐aryl 2‐indoles was found to be essential for high enantioselectivity products. This could due additional interaction between ester and catalyst, well intramolecular hydrogen bonding. Our findings provide new strategy asymmetric construction atropisomers.

Language: Английский

Citations

12