Atroposelective Synthesis of Heterobiaryls through Ring Formation DOI

Huai‐Ri Sun,

Atif Sharif,

Jie Chen

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(27)

Published: March 6, 2023

Atropisomeric heterobiaryls play a vital role in natural products, chiral ligands, organocatalysts, and other research fields, which have aroused great interest from chemists recent years. Until now, growing number of optically active based on indole, quinoline, isoquinoline, pyridine, pyrrole, azole, benzofuran skeletons been successfully synthesized through metal or organic catalytic cross-coupling, functionalization prochiral racemic heterobiaryls, ring formation. Among different strategies for the atroposelective synthesis strategy formation has become tool toward this goal. In review, we summarize enantioselective axially approaches, such as cycloaddition, cyclization, chirality conversion. Meanwhile, reaction mechanism corresponding applications are also discussed.

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

91
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

83
Progress in organocatalytic asymmetric (4+3) cycloadditions for the enantioselective construction of seven-membered rings DOI
Wei Tan, Jiayi Zhang,

Cong‐Hui Gao

et al.

Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(4), P. 966 - 992

Published: Feb. 15, 2023

Language: Английский

Citations

82
Photoinduced Cobalt-Catalyzed Desymmetrization of Dialdehydes to Access Axial Chirality DOI
Hao Jiang,

Xiang‐Kui He,

Xuan‐Feng Jiang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(12), P. 6944 - 6952

Published: March 15, 2023

Enantioselective metallaphotoredox catalysis, which combines photoredox catalysis and asymmetric transition-metal has become an effective approach to achieve stereoconvergence under mild conditions. Although many impressive synthetic approaches have been developed access central chirality, the construction of axial chirality by still remains underexplored. Herein, we report two visible light-induced cobalt-catalyzed reductive couplings biaryl dialdehydes synthesize axially chiral aldehydes (60 examples, up 98% yield, >19:1 dr, >99% ee). This protocol shows good functional group tolerance, broad substrate scope, excellent diastereo- enantioselectivity.

Language: Английский

Citations

82
Catalytic Asymmetric Synthesis of Axially Chiral Diaryl Ethers through Enantioselective Desymmetrization DOI

Hanyang Bao,

Yunrong Chen, Xiaoyu Yang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(14)

Published: Feb. 10, 2023

Axially chiral diaryl ethers are a type of unique atropisomers bearing two potential axes, which have applications in variety research fields. However, the catalytic enantioselective synthesis these ether is largely underexplored when compared to asymmetric biaryl or other types atropisomers. Herein, we report highly efficient through an organocatalyzed desymmetrization protocol. The phosphoric acid-catalyzed electrophilic aromatic aminations symmetrical 1,3-benzenediamine substrates afforded series excellent yields and enantioselectivities. facile construction heterocycles by utilizations 1,2-benzenediamine moiety products provided access structurally diverse novel azaarene-containing

Language: Английский

Citations

50
Enantioselective Strategies for The Synthesis of N−N Atropisomers DOI Creative Commons
Giovanni Centonze, Chiara Portolani, Paolo Righi

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(31)

Published: April 25, 2023

Axially chiral compounds have been always considered a laboratory curiosity with rare prospects of being applied in asymmetric synthesis. Things changed very quickly the last twenty years when it was understood important role and enormous impact that these medicinal, biological material chemistry. The synthesis atropisomers became rapidly expanding field recent reports on development N-N strongly prove how this research is hot topic open to new challenges frontiers This review focuses advances enantioselective highlighting strategies breakthroughs obtain novel stimulating atropisomeric framework.

Language: Английский

Citations

49
Atroposelective catalysis DOI

Tanno A. Schmidt,

Valeriia Hutskalova,

Christof Sparr

et al.

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: 8(7), P. 497 - 517

Published: June 18, 2024

Language: Английский

Citations

21
Enantioselective Synthesis of Axially Chiral Alkylidenecycloalkanes via Copper-Catalyzed Functionalization of Acyl Allenols DOI

Baihui Gong,

Qing‐Bin Lu,

R. Li-jiun Sun

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 2351 - 2358

Published: Jan. 24, 2025

Language: Английский

Citations

3
Asymmetric Hydrophosphinylation of Alkynes: Facile Access to Axially Chiral Styrene‐Phosphines DOI
Baohua Cai, Yuan Cui, Jian Zhou

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(3)

Published: Nov. 25, 2022

Abstract A Cu/CPA co‐catalytic system has been developed for achieving the direct hydrophosphinylation of alkynes with phosphine oxides in delivering novel axially chiral phosphorus‐containing alkenes high yields and excellent enantioselectivities (up to 99 % yield ee). DFT calculations were performed elucidate reaction pathway origin enantiocontrol. This streamlined modular methodology establishes a new platform design application styrene‐phosphine ligands.

Language: Английский

Citations

49
Enantioselective Access to Triaryl-2-pyrones with Monoaxial or Contiguous C–C Diaxes via Oxidative NHC Catalysis DOI

Si-Chen Zhang,

Shengping Liu, Xia Wang

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(4), P. 2565 - 2575

Published: Feb. 6, 2023

We present herein an unprecedented stereoselective synthesis of triaryl-2-pyrones with monoaxial or contiguous diaxes from readily available starting materials. This N-heterocyclic carbene catalysis method adopts atroposelective annulation 2-aryketones ynals under oxidative conditions. The includes the construction one two axes in a single operation, achieves step economy, and affords axially chiral moderate to good yields, high excellent enantioselectivities. DFT calculations relative energies stereoisomers rotational barriers were performed.

Language: Английский

Citations

43