Atropisomers beyond the C–C axial chirality: Advances in catalytic asymmetric synthesis

Chem, Journal Year: 2022, Volume and Issue: 8(7), P. 1855 - 1893

Published: May 6, 2022

Language: Английский

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Synthesis of axially chiral alkenylboronates through combined copper- and palladium-catalysed atroposelective arylboration of alkynes

Nature Synthesis, Journal Year: 2023, Volume and Issue: 2(2), P. 140 - 151

Published: Jan. 5, 2023

Language: Английский

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Catalytic Asymmetric Synthesis of Axially Chiral Diaryl Ethers through Enantioselective Desymmetrization

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

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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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Catalytic atroposelective synthesis

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

Published: April 30, 2024

Language: Английский

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Asymmetric synthesis of N–N axially chiral compounds via organocatalytic atroposelective N-acylation

Chemical Science, Journal Year: 2021, Volume and Issue: 13(1), P. 141 - 148

Published: Nov. 24, 2021

A highly efficient atroposelective N -acylation reaction of quinazolinone type benzamides with cinnamic anhydrides for the direct catalytic synthesis optically active atropisomeric derivatives was developed.

Language: Английский

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Enantioselective Cobalt-Catalyzed Cascade Hydrosilylation and Hydroboration of Alkynes to Access Enantioenriched 1,1-Silylboryl Alkanes

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(33), P. 13124 - 13134

Published: Aug. 12, 2021

Enantioenriched 1,1-silylboryl alkanes possess silyl and boryl groups that are both connected to the same stereogenic carbon center at well-defined orientations. As these chiral multifunctionalized compounds potentially offer two synthetic handles, they highly valued building blocks in asymmetric synthesis as well medicinal chemistry. Despite potential usefulness, efficient approaches for their preparation scarce. Seeking address this deficiency, an enantioselective cobalt-catalyzed hydrosilylation/hydroboration cascade of terminal alkynes has been realized. This protocol constitutes impressive case chemo-, regio-, stereoselectivity wherein different hydrofunctionalization events exquisitely controlled by a single set metal catalyst ligand, operation which would usually require separate catalytic systems. Downstream transformations enantioenriched 1,1-silyboryl led various valuable compounds. Mechanistic studies suggest present reaction undergoes regioselective stereocontrolled sequential hydrosilylation hydroboration processes.

Language: Английский

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A Dynamic Kinetic Resolution Approach to Axially Chiral Diaryl Ethers by Catalytic Atroposelective Transfer Hydrogenation

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

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Construction of C-B axial chirality via dynamic kinetic asymmetric cross-coupling mediated by tetracoordinate boron

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: July 24, 2023

Abstract Catalytic dynamic kinetic asymmetric transformation (DyKAT) provides a powerful tool to access chiral stereoisomers from racemic substrates. Such has been widely employed on the construction of central chirality, however, application in axial chirality remains underexplored because its equilibrium substrate enantiomers is limited five-membered metalacyclic intermediate. Here we report tetracoordinate boron-directed cross-coupling racemic, configurationally stable 3-bromo-2,1-azaborines with boronic acid derivatives. A series challenging C-B axially compounds were prepared generally good excellent enantioselectivities. Moreover, this can also be extended prepare atropisomers bearing adjacent and C-C diaxes diastereo- enantio-control. The key success relies rational design reversible boron intermediate, which supported by theoretical calculations that dramatically reduces rotational barrier original axis achieves goal DyKAT.

Language: Английский

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Enantioselective Synthesis of Axially Chiral Diaryl Ethers via NHC Catalyzed Desymmetrization and Following Resolution

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(4)

Published: Nov. 29, 2023

Axially chiral diaryl ethers are present in numerous natural products and bioactive molecules. However, only few catalytic enantioselective approaches have been established to access ether atropisomers. Herein, we report the N-heterocyclic carbene-catalyzed synthesis of axially via desymmetrization prochiral 2-aryloxyisophthalaldehydes with aliphatic alcohols, phenol derivatives, heteroaromatic amines. This reaction features mild conditions, good functional group tolerance, broad substrate scope excellent enantioselectivity. The utility this methodology is illustrated by late-stage functionalization, gram-scale synthesis, diverse enantioretentive transformations. Control experiments DFT calculations support association NHC-catalyzed following kinetic resolution enhance

Language: Английский

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