Synthesis of Axially Chiral Biaryls through Sulfoxide-Directed Asymmetric Mild CH Activation and Dynamic Kinetic Resolution

2014 ◽  
Vol 53 (50) ◽  
pp. 13871-13875 ◽  
Author(s):  
Chinmoy Kumar Hazra ◽  
Quentin Dherbassy ◽  
Joanna Wencel-Delord ◽  
Françoise Colobert
Keyword(s):  
Kinetic Resolution ◽  
Dynamic Kinetic Resolution ◽  
Axially Chiral

Atroposelective Transfer Hydrogenation of Biaryl Aminals via Dynamic Kinetic Resolution. Synthesis of Axially Chiral Diamines

ACS Catalysis ◽  
2021 ◽  
pp. 4117-4124
Author(s):  
José A. Carmona ◽  
Carlos Rodríguez-Franco ◽  
Joaquín López-Serrano ◽  
Abel Ros ◽  
Javier Iglesias-Sigüenza ◽  
...  
Keyword(s):  
Kinetic Resolution ◽  
Transfer Hydrogenation ◽  
Dynamic Kinetic Resolution ◽  
Axially Chiral ◽  
Chiral Diamines

Organocatalytic Asymmetric Methodologies towards the Synthesis of Atropisomeric N-Heterocycles

Synthesis ◽  
2020 ◽  
Vol 52 (17) ◽  
pp. 2450-2468
Author(s):  
Vasco Corti ◽  
Giulio Bertuzzi
Keyword(s):  
Kinetic Resolution ◽  
Dynamic Kinetic Resolution ◽  
Chirality Transfer ◽  
Axial Chirality ◽  
Axially Chiral ◽  
Molecular Architectures

A perspective on the literature dealing with the organocatalytic asymmetric preparation of axially chiral N-heterocycles is provided. A particular focus is devoted to rationalize the synthetic strategies employed in each case. Moreover, specific classes of organocatalysts are shown to stand out as privileged motives for the stereoselective preparation of such synthetically challenging molecular architectures. Finally, an overview of the main trends in the field is given.1 Introduction2 Five-Membered Rings2.1 Arylation2.2 Dynamic Kinetic Resolution2.3 Ring Construction2.4 Central-to-Axial Chirality Conversion and Chirality Transfer2.5 Desymmetrization3 Six-Membered Rings3.1 Desymmetrization3.2 (Dynamic) Kinetic Resolution3.3 Ring Construction3.4 Central-to-Axial Chirality Conversion4 Conclusion

Catalytic Atroposelective Dynamic Kinetic Resolution of Substituted Indoles

Synlett ◽  
2021 ◽  
Author(s):  
Ahreum Kim ◽  
Yongseok Kwon
Keyword(s):  
Asymmetric Catalysis ◽  
Kinetic Resolution ◽  
Ortho Position ◽  
Dynamic Kinetic Resolution ◽  
Research Attention ◽  
Considerable Research ◽  
Chiral Phosphoric Acid ◽  
Axially Chiral ◽  
High Yields ◽  
Enantioselective Syntheses

Advances in asymmetric catalysis have led to enormous progress in the atroposelective synthesis of axially chiral biaryls. Because of the biological importance of indoles, stereogenic axes in aryl-substituted indoles have attracted considerable research attention in recent years. Here we present a summary of recent advances in the atroposelective synthesis of aryl-substituted indoles by dynamic kinetic resolution. While several researchers have developed enantioselective syntheses of 3-arylindoles, N-arylindoles have been much less studied. Accordingly, we have reported a Pictet–Spengler reaction with catalytic and enantioselective control of the axial chirality around the C−N bond of the product. A chiral phosphoric acid induces the cyclization smoothly and with high yields and excellent enantioselectivities. To achieve this high selectivity, an NH group at the ortho position of the N-substituted aromatic ring that interacts favorably with the catalyst is required. Furthermore, when substituted aldehydes are used instead of paraformaldehyde, both the point and axial chiralities can be controlled during the cyclization.

scholarly journals Atroposelective transformation of axially chiral (hetero)biaryls. From desymmetrization to modern resolution strategies

2021 ◽  
Author(s):  
José A. Carmona ◽  
Carlos Rodríguez-Franco ◽  
Rosario Fernández ◽  
Valentín Hornillos ◽  
José M. Lassaletta
Keyword(s):  
Kinetic Resolution ◽  
Starting Material ◽  
Dynamic Kinetic Resolution ◽  
Axially Chiral ◽  
Asymmetric Transformation ◽  
And Behavior ◽  
Resolution Strategies

Atroposelective transformations of (hetero)biaryls are classified into desymmetrization, kinetic resolution, dynamic kinetic resolution, and dynamic kinetic asymmetric transformation depending on the nature and behavior of the starting material.

scholarly journals Catalytic atroposelective synthesis of axially chiral benzonitriles via chirality control during bond dissociation and CN group formation

2022 ◽  
Vol 13 (1) ◽  
Author(s):  
Ya Lv ◽  
Guoyong Luo ◽  
Qian Liu ◽  
Zhichao Jin ◽  
Xinglong Zhang ◽  
...  
Keyword(s):  
Dft Calculations ◽  
Kinetic Resolution ◽  
Group Formation ◽  
Heterocyclic Carbenes ◽  
Large Set ◽  
Dynamic Kinetic Resolution ◽  
Catalytic Activities ◽  
Bond Dissociation ◽  
Axially Chiral ◽  
Chirality Control

AbstractThe applications of axially chiral benzonitriles and their derivatives remain mostly unexplored due to their synthetic difficulties. Here we disclose an unusual strategy for atroposelective access to benzonitriles via formation of the nitrile unit on biaryl scaffolds pre-installed with stereogenic axes in racemic forms. Our method starts with racemic 2-arylbenzaldehydes and sulfonamides as the substrates and N-heterocyclic carbenes as the organocatalysts to afford axially chiral benzonitriles in good to excellent yields and enantioselectivities. DFT calculations suggest that the loss of p-toluenesulfinate group is both the rate-determining and stereo-determining step. The axial chirality is controlled during the bond dissociation and CN group formation. The reaction features a dynamic kinetic resolution process modulated by both covalent and non-covalent catalytic interactions. The axially chiral benzonitriles from our method can be easily converted to a large set of functional molecules that show promising catalytic activities for chemical syntheses and anti-bacterial activities for plant protections.

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