Catalytic Asymmetric Synthesis of Atropisomers Bearing Multiple Chiral Elements: An Emerging Field

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

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Atroposelective Construction of Carbon–Boron Axial Chirality through Rh-Catalyzed [2 + 2 + 2] Cycloaddition

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 5064 - 5076

Published: March 20, 2024

Axially chiral compounds have widespread applications in many fields. While significant progress has been made for the asymmetric synthesis of atropisomers consisting C–C bonds, an efficient approach construction C–B is still lacking. Herein, we report a practical method atroposelective axially arylboron through Rh-catalyzed [2 + 2 2] cycloaddition. The reaction exhibits broad substrate scope and good functional group tolerance, thus providing protocol to access variety high yields enantiocontrol. utility these adequately demonstrated by versatile transformations into highly valuable such as phosphine ligands fluorescent molecules. Mechanistic experiments DFT calculations provided insights mechanism well origin

Language: Английский

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Development of Configurationally Labile Biaryl Reagents for Atropisomer Synthesis

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

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Atroposelective synthesis of biaxial bridged eight-membered terphenyls via a Co/SPDO-catalyzed aerobic oxidative coupling/desymmetrization of phenols

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

Published: May 30, 2024

Abstract Bridged chiral biaryls are axially compounds with a medium-sized ring connecting the two arenes. Compared plentiful methods for enantioselective synthesis of biaryl compounds, synthetic approaches this subclass bridged atropisomers limited. Here we show an atroposelective 1,3-diaxial eight-membered terphenyl through Co/SPDO (spirocyclic pyrrolidine oxazoline)-catalyzed aerobic oxidative coupling/desymmetrization reaction prochiral phenols. This catalytic desymmetric process is enabled by combination earth-abundant Co(OAc) 2 and unique SPDO ligand in presence DABCO (1,4-diaza[2.2.2]bicyclooctane). An array diaxial terphenyls embedded azocane can be accessed high yields (up to 99%) excellent enantio- (>99% ee) diastereoselectivities (>20:1 dr).

Language: Английский

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Axially Chiral Bridged Biaryls by Ni-Catalyzed Kinetic Asymmetric C–O Bond Cleavage

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 8176 - 8183

Published: May 10, 2024

Axially chiral bridged biaryls represent an important subset of axially biaryl scaffolds in fields ranging from organic synthesis to biochemistry materials science. While numerous catalytic strategies have been elucidated for the construction axial chirality, enantioenriched form remains underdeveloped. Herein, we demonstrate approach synthesize diverse through nickel-catalyzed kinetic asymmetric cleavage unactivated aromatic C–O bond. The system features mild reaction conditions, high resolution efficiency, and versatile post-functionalizations. Mechanistic studies reveal impact nickel catalyst's chirality on stereochemical output this transformation.

Language: Английский

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The literature of heterocyclic chemistry, part XXII, 2022

Advances in heterocyclic chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Language: Английский

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Access to Chiral Bridged Biaryls via Brønsted Acid-Catalyzed Asymmetric Addition of Alcohols to Fluoroalkylated Biaryl Oxazepines

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 24, 2025

We disclose herein a chiral phosphoric-acid-catalyzed enantioselective addition reaction of alcohols to fluoroalkylated biaryl 1,3-oxoazepines, which furnished wide range bridged biaryls bearing quaternary carbon stereocenter on the seven-membered ring in high yields (up 99%) with excellent enantioselectivities 98% ee). Our method can be used for modification several natural products and bioactive molecules. Preliminary studies revealed that obtained this exhibit good vitro bioactivities against two plant pathogens.

Language: Английский

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Synthesis of All Ring Sizes of Medium-Sized Heterocycles Bridged Biaryls via VQM-Enabled Diversity-Oriented Synthetic Strategy

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 25, 2025

Herein, for the first time, controllable, accurate, and diverse synthesis of all ring sizes medium-sized (8- to 11-membered) indole-derived bridged biaryls has been realized by using ingeniously designed o-alkynylnaphthols that feature cyclic amines with adjustable sizes. The transformation may proceed through a DBN-mediated in-situ generation vinylidene ortho-quinone methides/indole-ring formation/ring expansion cascade sequence, which is characterized acceptable excellent yields good functional group tolerance.

Language: Английский

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Enhanced Pyridine-Oxazoline Ligand-Enabled Pd(II)-Catalyzed Aminoacetoxylation of Alkenes for the Asymmetric Synthesis of Biaryl-Bridged 7-Membered N-Heterocycles and Atropisomers

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

A new class of binaphthyl unit-enhanced pyridine-oxazoline ligands was developed to promote the Pd-catalyzed enantioselective intramolecular 7-exo aminoacetoxylation unactivated biaryl alkenes. Biaryl-bridged 7-membered N-heterocycles bearing a chiral center were obtained in good yields with excellent enantioselectivities (up 99:1 er). Computational investigations on series biaryl-bridged rings provided insights into rotational barrier potentially unit by substituent effect including heteroatom, protecting group, and center. The kinetic resolution racemic axially biaryls via alkenes has also been achieved, affording previously inaccessible both axis, as well amino alcohols.

Language: Английский

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Inherently Chiral Seven- and Eight-Membered Rings: Enantioselective Synthesis and Applications

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 17, 2025

Compared to smaller or larger rings, seven- and eight-membered carbo- heterocycles are typically nonplanar exhibit greater conformational rigidity. This property alone can impart chirality certain 7- 8-membered ring systems. Herein, we summarize recent achievements in the enantioselective synthesis of this class inherently chiral medium including both construction modification, as well applications ligands catalysts derived from these rigid cyclic scaffolds asymmetric catalysis.

Language: Английский

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