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

Hanyang Bao,

Yunrong Chen, Xiaoyu Yang

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(14)

Published: Feb. 10, 2023

Abstract 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

Stereodynamic Strategies to Induce and Enrich Chirality of Atropisomers at a Late Stage DOI
Casey B. Roos, Chang-Hwa Chiang, Lauren A. M. Murray

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(17), P. 10641 - 10727

Published: Aug. 28, 2023

Enantiomers, where chirality arises from restricted rotation around a single bond, are atropisomers. Due to the unique nature of origins their chirality, synthetic strategies access these compounds in an enantioselective manner differ those used prepare enantioenriched containing point arising unsymmetrically substituted carbon center. In particular stereodynamic transformations, such as dynamic kinetic resolutions, thermodynamic and deracemizations, which rely on ability racemize or interconvert enantiomers, promising set transformations optically pure late stage sequence. Translation approaches with atropisomers requires expanded toolbox for epimerization/racemization provides opportunity develop new conceptual framework synthesis compounds.

Language: Английский

Citations

51
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

48
Catalytic atroposelective synthesis DOI
Shao‐Hua Xiang, Wei‐Yi Ding, Yong‐Bin Wang

et al.

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(5), P. 483 - 498

Published: April 30, 2024

Language: Английский

Citations

31
Enantioselective Synthesis of Planar‐Chiral Sulfur‐Containing Cyclophanes by Chiral Sulfide Catalyzed Electrophilic Sulfenylation of Arenes DOI

Deng Zhu,

Tong Mu,

Ze‐Long Li

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(10)

Published: Jan. 17, 2024

Abstract An efficient catalytic asymmetric electrophilic sulfenylation reaction for the synthesis of planar‐chiral sulfur‐containing cyclophanes has been developed first time. This was achieved by using a new Lewis base catalyst and ortho ‐trifluoromethyl‐substituted sulfenylating reagent. Using substrates with low rotational energy barrier, transformation proceeded through dynamic kinetic resolution, high barrier allowed to undergo resolution process. Meanwhile, this compatible desymmetrization process when symmetric were used. Various readily obtained in moderate excellent yields enantioselectivities (up 97 % yield 95 ee). approach used synthesize pharmaceutically relevant molecules. Density functional theory calculations showed that π‐π interactions between sulfenyl group aromatic ring substrate play crucial role enantioinduction reaction.

Language: Английский

Citations

18
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

48
Atroposelective Synthesis of Diarylamines via Organocatalyzed Electrophilic Amination DOI

Zidan Ye,

Wansen Xie,

Donglei Wang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 4958 - 4967

Published: March 18, 2024

Axially chiral diarylamine atropisomers represent a distinct category characterized by two contiguous C–N axes, which exhibit significantly lower racemization barrier due to the concerted rotation of both axes. In this work, we introduce an effective method for atroposelective synthesis axially diarylamines through organocatalyzed asymmetric electrophilic amination with azodicarboxylates, afforded variety acyclic secondary in good yields high enantioselectivities. This expands scope catalytic beyond N-aryl quinoid-type atropisomers, enabling without constraining one axis intramolecular hydrogen bonding. Both experimental and computational studies show minimal contribution bonding stabilizing configurations these undergo via

Language: Английский

Citations

9
Atroposelective Sulfenylation of Biaryl Anilines Catalyzed by Chiral SPINOL-Derived Selenide DOI

Xin-Yu Zhang,

Deng Zhu,

Yu-Xuan Huo

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(19), P. 3445 - 3450

Published: May 11, 2023

The atroposelective electrophilic sulfenylation of biaryl anilines has been realized for the first time. reaction is enabled by a new chiral 6,6'-dianisole substituted SPINOL-derived selenide. A variety axially sulfur-containing aniline compounds were obtained in moderate to excellent yields with enantioselectivities. experimental results suggest that catalyst rigidity important high atroposelectivity.

Language: Английский

Citations

21
Enantioselective Synthesis of “NO2···NH” Hydrogen Bond-Stabilized C–N Axially Chiral Diarylamines DOI
Wei Lin,

Yingbo Shao,

Zeyang Hao

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(2), P. 1183 - 1192

Published: Jan. 9, 2024

Herein, N-nucleophilic tandem oxidation–N-arylation–oxidation reaction and C-nucleophilic bromination of substituted anilines have been developed using chiral phosphoric acid catalysis, enabling access to axially diarylamines. The key feature this strategy is that the "NO2···H–N" hydrogen bond was successfully introduced into acyclic diaryl secondary amines, which contain two potential contiguous atropisomeric C–N axes, stabilize one planar axial conformations. This methodology provided a series optically pure diarylamine atropisomers containing new type in good yields (up 99%) high enantiomeric ratios 99.5:0.5 e.r.). synthetic utility demonstrated through large-scale reactions transformations products. Plausible models were proposed explain enantioselectivity

Language: Английский

Citations

7
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
Enantioselective Synthesis of Axially Chiral Diaryl Ethers through Chiral Phosphoric Acid-Catalyzed Desymmetric Acylation with Azlactones DOI
Jiawei Xu, Wei Lin, Hanliang Zheng

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(9), P. 6667 - 6673

Published: April 16, 2024

C–O axially chiral diaryl ethers play important roles in natural products and bioactive molecules, but because of the low rotational barrier strict steric hindrance requirements, catalytic asymmetric construction still remains a challenge. Herein, we devised strategy employing achiral azlactone for desymmetrization prochiral diamines under catalysis phosphoric acid. The targeted were obtained very good yields (up to 98%) high enantioselectivities >99.5:0.5 er). synthetic utility was demonstrated through large-scale reaction transformations products. Moreover, DFT calculations conducted probe origins enantioselectivity.

Language: Английский

Citations

5