Synthesis of Chiral Axially Diaryl Aldehydes by Chiral Phosphoric Acid Catalyzed Desymmetrization Reaction DOI

Lutong Yuan,

Lixin Cui,

Yuheng Liu

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 29, 2024

Abstract Axially chiral biaryl aldehydes are precursors for the synthesis of axially compounds and novel catalysts great interest, which play vital roles in extensive research fields. However, limited strategies exist efficient aldehydes, construction structurally diverse remains challenging. Herein, a strategy is reported with varying structures from dialdehydes aromatic amines presence phosphoric acid catalyst. This protocol features excellent enantioselectivity, mild conditions, good functional‐group tolerance.

Language: Английский

Axially chiral alkenes: Atroposelective synthesis and applications DOI Creative Commons

San Wu,

Shao‐Hua Xiang, Jun Kee Cheng

et al.

Tetrahedron Chem, Journal Year: 2022, Volume and Issue: 1, P. 100009 - 100009

Published: March 1, 2022

Axial chirality is historically epitomized by biaryl compounds containing rotationally impeded aryl-aryl linkage. As the field of atroposelective catalysis advances, synthesis and application less common scaffolds such as alkenes have now come to fore. The manifestation axial in aryl was hypothesized 1928 first resolution achieved nearly a decade later. However, catalytic asymmetric construction axially chiral open-chain appeared only 2017 which ushered renewed focus on these structures. In principle, possess an alkene group tethered at one end stereogenic axis, greatly reduces overall rigidity. To date, atropisomers with C (vinyl)-C (aryl) (vinyl)-heteroatom bond been reported. Considering rapid growth synthetic utility alkenes, this review intends provide historical overview discusses new developments. It hope that timely discussion would motivate continued nascent field.

Language: Английский

Citations

74
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
Synthetic strategies and mechanistic studies of axially chiral styrenes DOI Creative Commons

Zi-Hao Li,

Quan‐Zhe Li,

He‐Yuan Bai

et al.

Chem Catalysis, Journal Year: 2023, Volume and Issue: 3(6), P. 100594 - 100594

Published: April 6, 2023

Language: Английский

Citations

27
Organocatalytic Atroposelective Dynamic Kinetic Resolution Involving Ring Manipulations DOI

Qin Shi,

Fang Fang, Dao‐Juan Cheng

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(6), P. 1269 - 1284

Published: Jan. 31, 2024

Abstract Axially chiral architectures exist widely in natural products, biologically relevant molecules, ligands and catalysts as well functional materials. Therefore, catalytic asymmetric synthesis of atropisomers has become one the most fast‐growing fields community chemistry rapid advances have occurred. Among different methods reported, organocatalytic atroposelective dynamic kinetic resolution (DKR) involving ring manipulations stands out a cutting‐edge technology to construct axial chirality from point atom/step economy. In this DKR strategy, configurational lability starting materials originates chirally‐labile structure cyclic substrates/intermediates or transient formation through noncovalent interactions acyclic substrates. The two material are equilibrium reaction medium, ensuring constant transformation less reactive atropisomer into more one, then single enantiopure product presence an appropriate organocatalyst. This review summarizes recent advancements on topic, including their scopes, limitations, mechanisms, applications provides some insights further developments.

Language: Английский

Citations

11
Recent advances in organocatalytic atroposelective reactions DOI Creative Commons

Henrich Szabados,

Radovan Šebesta

Beilstein Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 21, P. 55 - 121

Published: Jan. 9, 2025

Axial chirality is present in a variety of naturally occurring compounds, and becoming increasingly relevant also medicine. Many axially chiral compounds are important as catalysts asymmetric catalysis or have chiroptical properties. This review overviews recent progress the synthesis via organocatalysis. Atroposelective organocatalytic reactions discussed according to dominant catalyst activation mode. For covalent organocatalysis, typical enamine iminium modes presented, followed by N -heterocyclic carbene-catalyzed reactions. The bulk devoted non-covalent activation, where Brønsted acids feature most prolific catalytic structure. last part article discusses hydrogen-bond-donating other motifs such phase-transfer catalysts.

Language: Английский

Citations

1
Copper-catalysed dynamic kinetic asymmetric C−O cross-coupling to access chiral aryl oxime ethers and diaryl ethers DOI Creative Commons

Meiru Zhang,

Haoran Wang,

Hui-Mei Shan

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: March 13, 2025

Dynamic kinetic resolution (DKR) has emerged as an elegant and powerful tool for enantioselective synthesis, enabling the transformation of racemic compounds into enantiomerically enriched products with theoretically quantitative yields. Despite its widespread success, dynamic asymmetric C−O cross-coupling presented significant challenges remains unexplored. In this study, we report a oximes phenols via copper/BOX-catalysed O-arylation diaryliodonium salts. This method efficiently produces wide range inherently chiral oxime ethers, well axially styrenes, high yields excellent regio- enantioselectivities. Through controlled experiments Density Functional Theory (DFT) studies, have elucidated process gained insights origins enantioselectivity. The Here, authors

Language: Английский

Citations

1
Development of Configurationally Labile Biaryl Reagents for Atropisomer Synthesis DOI
Changhui Wu, Jin Yang,

Xiaoyuan Zhang

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(28)

Published: May 16, 2024

Abstract Axially chiral biaryl scaffolds are important in pharmaceuticals, natural products, and asymmetric synthesis. Atroposelective ring‐opening of configurationally labile reagents via dynamic kinetic transformation provides a valuable approach to access axially atropisomers. This review summarizes seminal contributions recent advancements on this topic based the use different types reagents.

Language: Английский

Citations

6
Synthesis of aryl-fused 1,4-oxathiepines from pyridinium 1,4-zwitterionic thiolates and vinylideneortho-quinone methides DOI

Yixuan He,

Ping Wu,

Xiang Zhang

et al.

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(17), P. 4612 - 4618

Published: Jan. 1, 2022

Synthesis of aryl-fused 1,4-oxathiepines from pyridinium 1,4-zwitterionic thiolates with vinylidene ortho -quinone methides generated in situ via a formal (3 + 4) pathway.

Language: Английский

Citations

21
Asymmetric allylic substitution-isomerization for accessing axially chiral vinylindoles by intramolecular π … π stacking interactions DOI

Ying-Xiang Wu,

Qi Liu, Qiang Zhang

et al.

Cell Reports Physical Science, Journal Year: 2022, Volume and Issue: 3(8), P. 101005 - 101005

Published: Aug. 1, 2022

Language: Английский

Citations

19
Asymmetric Reductive Amination in Organocatalysis and Biocatalysis DOI
Tingting Li, Qian Zhou,

Fanjing Meng

et al.

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 26(37)

Published: July 5, 2023

Abstract This review summarizes the recent progress of organocatalytic and biocatalytic asymmetric reductive amination (ARA), a challenging but important topic for drug discovery pharmaceutical industry. At present, ARA can be divided into three categories: metal catalysis, organic biocatalysis. In past decade, transition metal‐catalysed has been well established. Organocatalytic emerged as powerful alternative to ARA, hydrogen sources used in are usually Hantzsch esters, benzothiazolines, boranes, hydrosilanes, which require Lewis base or phosphoric acid catalysts activate them give secondary chiral amines. It is worth mentioning that made remarkable last amino dehydrogenases, amine opine dehydrogenases imine reductases have successfully ARA.

Language: Английский

Citations

9