Catalytic Enantioselective Synthesis of Axially Chiral Diaryl Ethers Via Asymmetric Povarov Reaction Enabled Desymmetrization DOI Creative Commons

Zidan Ye,

Wansen Xie,

Wei Liu

et al.

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

Published: July 16, 2024

Axially chiral diaryl ethers represent a distinct class of atropisomers, characterized by unique dual C─O axes system, which have been found in variety natural products, pharmaceuticals, and ligands. However, the catalytic enantioselective synthesis these atropoisomers poses significant challenges, due to difficulty controlling both axes, their more flexible conformations. Herein, an efficient protocol for axially is presented using organocatalyzed asymmetric Povarov reaction-enabled desymmetrization, followed aromatizations. This method yields wide range novel quinoline-based ether good high enantioselectivities. Notably, various aromatization protocols are developed, resulting diverse set polysubstituted quinoline-containing atropisomers. Thermal racemization studies suggested excellent configurational stabilities atropisomers (with barriers up 38.1 kcal mol

Language: Английский

Catalytic Enantioselective Synthesis of Inherently Chiral Molecules: Recent Advances DOI

Mengyao Tang,

Xiaoyu Yang

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 26(42)

Published: Sept. 2, 2023

Abstract Inherent chirality represents a distinct category of molecular that does not fall within the traditional classification four chiral elements: central, axial, planar, and helical chirality. While extensive research has been conducted on catalytic enantioselective construction these conventional chiralities, corresponding synthesis inherently molecules remained largely unexplored. This minireview provides comprehensive summary recent advancements in this field, focusing asymmetric calixarenes, saddle‐shaped tetraphenylenes their heterocycle derivatives, mechanically planar rotaxanes multilayer 3D frameworks, as well our perspective field.

Language: Английский

Citations

33
Organocatalytic Dynamic Kinetic Resolution Enabled Asymmetric Synthesis of Phosphorus‐Containing Chiral Helicenes DOI Open Access

Jia‐Hong Wu,

Siqiang Fang,

Xingtao Zheng

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(49)

Published: Oct. 17, 2023

The catalytic asymmetric synthesis of phosphorus-containing helicenes remains a formidable challenge, presumably due to the lack rational design substrates, right choice reactions together with highly effective catalysis systems. Herein, we disclosed an efficient and practical DKR-involving (dynamic kinetic resolution) cascade strategy toward synthesizing novel family phosphorus-installing by peptide-mimic phosphonium salt (PPS) catalysis. sequential process PPS-catalyzed phospha-Michael attack copper salt-facilitated aromatization led formation unprecedented oxa[5]helicene scaffolds. A wide variety substrates bearing assortment functional groups were compatible this protocol, furnishing expected helical compounds in high yields excellent stereoselectivities. Additionally, products could be conveniently elaborated promising phosphine ligands perfectly retained chirality, which turned out chiral transition metal-catalyzed reactions. These findings not only expand current library but also offer insights explore other challenging scaffolds molecular chirality.

Language: Английский

Citations

24
Enantioselective synthesis of molecules with multiple stereogenic elements DOI Creative Commons
Arthur Gaucherand, Expédite Yen‐Pon,

Antoine Domain

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(22), P. 11165 - 11206

Published: Jan. 1, 2024

This review explores the fascinating world of molecules featuring multiple stereogenic elements, unraveling different strategies designed over years for their enantioselective synthesis.

Language: Английский

Citations

15
Enantioselective synthesis of [4]helicenes by organocatalyzed intermolecular C-H amination DOI Creative Commons
Xihong Liu, Boyan Zhu, Xiaoyong Zhang

et al.

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

Published: Jan. 25, 2024

Abstract Catalytic asymmetric synthesis of helically chiral molecules has remained an outstanding challenge and witnessed fairly limited progress in the past decades. Current methods to construct such compounds almost entirely rely on catalytic enantiocontrolled fused-ring system extension. Herein, we report a direct terminal peri -functionalization strategy, which allows for efficient assembling 1,12-disubstituted [4]carbohelicenes via organocatalyzed enantioselective amination reaction 2-hydroxybenzo[ c ]phenanthrene derivates with diazodicarboxamides. The key feature this approach is that stereochemical information catalyst could be transferred into not only helix sense but also remote C-N axial chirality products, thus enabling [4]- [5]helicenes both structural diversity complexity good efficiency excellent enantiocontrol. Besides, large-scale preparations representative transformations helical products further demonstrate practicality protocol. Moreover, DFT calculations reveal hydrogen bonds C-H---π interactions between substrates contribute ideal control.

Language: Английский

Citations

13
Organocatalytic Enantioselective Synthesis of Inherently Chiral Calix[4]arenes DOI
Yukun Jiang,

Yongle Tian,

Jia Feng

et al.

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

Published: June 7, 2024

Inherently chiral calix[4]arenes are an excellent structural scaffold for enantioselective synthesis, recognition, sensing, and circularly polarized luminescence. However, their catalytic synthesis remains challenging. Herein, we report efficient of inherently calix[4]arene derivatives via cascade cyclization oxidation reactions. The three-component reaction features a broad substrate scope (33 examples), high efficiency (up to 90 % yield), enantioselectivity (>95 ee on average). potential applications highlighted by synthetic transformation detailed investigation photophysical chiroptical properties.

Language: Английский

Citations

12
Photocatalyst-free H2O-regulated and regiodivergent multicomponent hydrogenation/bifunctional sulfonylation of alkynes DOI
Jie Sun,

Chaodong Wang,

Chunlei Wu

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(6), P. 3301 - 3307

Published: Jan. 1, 2024

An efficient multicomponent reaction for the preparation of vinyl sulfone was achieved by hydrogenation/bifunctional sulfonylation alkynyl esters with N- allyl bromodifluoroacetamide, DABSO, and H 2 O under visible-light-only conditions.

Language: Английский

Citations

11
BINOL‐Based Chiral Macrocycles and Cages DOI

Yabing Yu,

Yaning Hu,

Chengbing Ning

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(29)

Published: May 6, 2024

Abstract Chirality, a fundamental principle in chemistry, biology, and medicine, is prevalent nature organisms. Chiral molecules, such as DNA, RNA, proteins, are crucial biomolecular synthesis, well the development of functional materials. Among these, 1,1′‐binaphthyl‐2,2′‐diol (BINOL) stands out for its stable chiral configuration, versatile functionality, commercial availability. BINOL widely employed asymmetric catalysis This review mainly focuses on recent research over past five years concerning use derivatives constructing macrocycles cages. Their contributions to luminescence, enantiomeric separation, transmembrane transport, were examined.

Language: Английский

Citations

11
Synthesis of Alkene Atropisomers with Multiple Stereogenic Elements via Catalytic Asymmetric Rearrangement of 3‐Indolylmethanols DOI
Ping Wu,

Wen‐Tao Zhang,

Jixiang Yang

et al.

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

Published: July 23, 2024

Abstract Catalytic enantioselective preparation of alkene atropisomers with multiple stereogenic elements and discovery their applications have become significant but challenging issues in the scientific community due to unique structures this class atropisomers. We herein report first catalytic atroposelective cyclopentenyl[ b ]indoles, a new kind atropisomers, point axial chirality via an unusual rearrangement reaction 3‐indolylmethanols under asymmetric organocatalysis. Notably, novel type promising developing chiral ligands or organocatalysts, discovering antitumor drug candidates fluorescence imaging materials. Moreover, theoretical calculations elucidated possible mechanism non‐covalent interactions control enantioselectivity. This approach offers synthetic strategy for elements, represents 3‐indolylmethanols, which will advance chemistry indole chemistry.

Language: Английский

Citations

9
An Overview of Recent Advances in Enantioselective Multicomponent Reactions DOI
Atieh Rezvanian,

Elham Mardi,

Pezhman Shiri

et al.

Journal of Molecular Structure, Journal Year: 2025, Volume and Issue: unknown, P. 141768 - 141768

Published: Feb. 1, 2025

Language: Английский

Citations

1
Helicoselective Synthesis of Indolohelicenoids through Organocatalytic Central‐to‐Helical Chirality Conversion DOI
Wenlei Xu,

Ru‐Xia Zhang,

Hui Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(9)

Published: Jan. 10, 2024

We report the helicoselective and convergent construction of indolohelicenoids with excellent efficiency stereocontrol. This reaction proceeds through a chiral-phosphoric-acid-catalyzed enantioselective cycloaddition eliminative aromatization sequence, which can be finely controlled by adjusting temperature. Mechanistic studies reveal that chiral phosphoric acid cooperatively serves as both bifunctional Brønsted catalyst, enabling one-pot central-to-helical chirality conversion. Additionally, optical properties synthesized were characterized to explore their potential applications in organic photoelectric materials.

Language: Английский

Citations

9