Recent Advances in Catalytic Asymmetric Construction of Atropisomers

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(8), P. 4805 - 4902

Published: March 27, 2021

Atropisomerism is a stereochemical behavior portrayed by three-dimensional molecules that bear rotationally restricted σ bond. Akin to the well-represented point-chiral molecules, atropisomerically chiral compounds are finding increasing utilities in many disciplines where molecular asymmetry influential. This provides steady demand on atroposelective synthesis, numerous synthetic pursuits have been rewarded with conceptually novel and streamlined methods while expanding structural diversity of atropisomers. review summarizes key achievements stereoselective preparation biaryl, heterobiaryl, nonbiaryl atropisomers documented between 2015 2020. Emphasis placed strategies for each class, examples cited illustrate potential applications accessed atropochiral targets.

Language: Английский

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Recent Developments in Enantioselective Transition Metal Catalysis Featuring Attractive Noncovalent Interactions between Ligand and Substrate

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(18), P. 10672 - 10714

Published: Aug. 14, 2020

Enantioselective transition metal catalysis is an area very much at the forefront of contemporary synthetic research. The development processes that enable efficient synthesis enantiopure compounds unquestionable importance to chemists working within many diverse fields central science. Traditional approaches solving this challenge have typically relied on leveraging repulsive steric interactions between chiral ligands and substrates in order raise energy one diastereomeric states over other. By contrast, Review examines alternative tactic which a set attractive noncovalent operating are used control enantioselectivity. Examples where creative approach has been successfully applied render fundamental enantioselective presented discussed. In cases examined, ligand scaffold carefully designed accommodate these interactions, while others, critical was only elucidated subsequent computational mechanistic studies. Through exploration discussion recent reports encompassing wide range reaction classes, we hope inspire continue develop asymmetric transformations based powerful concept.

Language: Английский

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The Catalytic Formation of Atropisomers and Stereocenters via Asymmetric Suzuki–Miyaura Couplings

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(9), P. 4918 - 4937

Published: April 12, 2022

Although Suzuki–Miyaura cross-coupling is one of the most convenient and well-developed reactions, its applications to asymmetric version deliver highly functionalized atropisomers or nonracemic coupling products have been less explored. Besides some excellent work reported intermittently, reaction remains a significant challenge, particularly for preparing heterocyclic atropisomers. A concise but critical knowledge on this topic may further inspire researchers across various subdisciplines develop innovative practical solutions tackle problem. Therefore, Review aims summarize pioneering cross-couplings cover implementations via homogeneous heterogeneous catalysis during recent years. Most notably, use transition metals other than palladium also described.

Language: Английский

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P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(14), P. 8657 - 8739

Published: July 2, 2024

Chiral phosphorus ligands play a crucial role in asymmetric catalysis for the efficient synthesis of useful optically active compounds. They are largely categorized into two classes: backbone chirality and P-stereogenic ligands. Most reported belong to former class. Privileged ones such as BINAP DuPhos frequently employed wide range catalytic transformations. In contrast, latter class has remained small family many years mainly because their synthetic difficulty. The late 1990s saw emergence novel with superior enantioinduction ability Rh-catalyzed hydrogenation reactions. Since then, numerous have been synthesized used This Review summarizes thus far, including stereochemical electronic properties that afford high excellent enantioselectivities. Examples reactions use this described together applications construction key intermediates natural products therapeutic agents. literature covered dates back 1968 up until December 2023, centering on studies published later years.

Language: Английский

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Enantioselective Synthesis of Axially Chiral Benzothiophene/Benzofuran‐Fused Biaryls by N‐Heterocyclic Carbene Catalyzed Arene Formation

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(25), P. 13918 - 13922

Published: April 14, 2021

Abstract Axially chiral biaryl scaffolds are prevalent in natural products, ligands, and organocatalysts. However, N‐heterocyclic carbene (NHC) catalyzed de novo construction of an aromatic ring with concomitant axial chirality induction for the synthesis atropisomers is far less developed, efficient axially tetra‐ ortho ‐substituted biaryls remains unsolved problem under NHC catalysis. Reported here NHC‐catalyzed benzothiophene/benzofuran‐fused from enals 2‐benzyl‐benzothiophene/benzofuran‐3‐carbaldehydes through a [2+4] annulation, decarboxylation, oxidative aromatization cascade central‐to‐axial conversion. The developed method provides general access to novel high enantioselectivities works well biaryls.

Language: Английский

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Enantioselective Synthesis of Axially Chiral Biaryls by Diels–Alder/Retro-Diels–Alder Reaction of 2-Pyrones with Alkynes

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(24), P. 8993 - 9001

Published: June 9, 2021

The enantioselective synthesis of axially chiral biaryls by a copper-catalyzed Diels–Alder/retro-Diels–Alder reaction 2-pyrones with alkynes is reported herein. Using electron-deficient and electron-rich 1-naphthyl acetylenes as the partners, broad range biaryl esters are obtained in excellent yields (up to 97% yield) enantioselectivities >99% ee). DFT calculations reveal mechanism provide insights into origins stereoselectivities. practicality robustness this showcased gram-scale synthesis. synthetic utilizations demonstrated amenable transformations products.

Language: Английский

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Catalytic Synthesis of Atropisomeric o-Terphenyls with 1,2-Diaxes via Axial-to-Axial Diastereoinduction

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(19), P. 7253 - 7260

Published: May 7, 2021

Herein, we report a modular and convergent strategy for the assembly of atropisomeric o-terphenyls with 1,2-diaxes via palladium/chiral norbornene cooperative catalysis axial-to-axial diastereoinduction. Readily available aryl iodides, 2,6-substituted bromides, potassium trifluoroborates are used as building blocks, laying foundation diversity-oriented synthesis these scaffolds (46 examples). Other features include unique diastereoinduction mode, construction two axes in single operation, step economy. DFT calculations performed to rationalize process. Synthetic utilities this method preparation oligophenyls, chiral catalysts, ligands demonstrated.

Language: Английский

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Construction of Axially Chiral Arylborons via Atroposelective Miyaura Borylation

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(27), P. 10048 - 10053

Published: June 28, 2021

Compared with the well-developed centrally chiral boron chemistry, C–B axially chemistry remains elusive and challenging. Herein we report first atroposelective Miyaura borylation of bromoarenes unsymmetrical diboron reagents for direct catalytic synthesis optically active atropisomeric arylborons. This reaction features broad substrate scope produces arylborons high yields good enantioselectivities.

Language: Английский

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Distal Ionic Substrate–Catalyst Interactions Enable Long-Range Stereocontrol: Access to Remote Quaternary Stereocenters through a Desymmetrizing Suzuki–Miyaura Reaction

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(1), P. 123 - 129

Published: Jan. 3, 2022

Spatial distancing of a substrate's reactive group and nonreactive catalyst-binding from its pro-stereogenic element presents substantial hurdles in asymmetric catalysis. In this context, we report desymmetrizing Suzuki–Miyaura reaction that establishes chirality at remote quaternary carbon. The anionic, chiral catalyst exerts stereocontrol through electrostatic steering substrates, even as the charged become increasingly distanced. This study demonstrates precise long-range is achievable by engaging ionic substrate–ligand interactions distal position.

Language: Английский

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Recent advances in the catalytic asymmetric construction of atropisomers by central-to-axial chirality transfer

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(8), P. 2280 - 2292

Published: Jan. 1, 2022

We highlighted the recent advances in field of central-to-axial chirality transfer for synthesis axially chiral molecules.

Language: Английский

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