Enantioselective desymmetrization reactions in asymmetric catalysis

Tetrahedron, Journal Year: 2022, Volume and Issue: 106-107, P. 132629 - 132629

Published: Jan. 1, 2022

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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Brønsted Acid Catalyzed Dearomatization by Intramolecular Hydroalkoxylation/Claisen Rearrangement: Diastereo‐ and Enantioselective Synthesis of Spirolactams

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(52), P. 27164 - 27170

Published: Oct. 21, 2021

Described herein is a novel Brønsted acid catalyzed intramolecular hydroalkoxylation/Claisen rearrangement, allowing the practical and atom-economic synthesis of range valuable spirolactams from readily available ynamides in generally good to excellent yields with diastereoselectivities broad substrate scope. Importantly, an unexpected dearomatization nonactivated arenes heteroaromatic compounds involved this tandem sequence. Moreover, asymmetric version cyclization was also achieved by efficient kinetic resolution chiral phosphoric catalysis. In addition, [3,3]-rearrangement shown be kinetically preferred over related [1,3]-rearrangement theoretical calculations.

Language: Английский

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An update on chiral phosphoric acid organocatalyzed stereoselective reactions

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(17), P. 3477 - 3502

Published: Jan. 1, 2023

This review article presents an in-depth analysis of the strategies and methodologies for using chiral phosphoric acids as organocatalysts in asymmetric syntheses from recent literature.

Language: Английский

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Catalytic Enantioselective Synthesis of Inherently Chiral Molecules: Recent Advances

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 26(42)

Published: Sept. 2, 2023

Abstract Inherent chirality represents a distinct category of molecular that does not fall within the traditional classification four chiral elements: central, axial, planar, and helical chirality. While extensive research has been conducted on catalytic enantioselective construction these conventional chiralities, corresponding synthesis inherently molecules remained largely unexplored. This minireview provides comprehensive summary recent advancements in this field, focusing asymmetric calixarenes, saddle‐shaped tetraphenylenes their heterocycle derivatives, mechanically planar rotaxanes multilayer 3D frameworks, as well our perspective field.

Language: Английский

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Chiral Phosphoric Acid–Palladium(II) Complex Catalyzed Asymmetric Desymmetrization of Biaryl Compounds by C(sp³)–H Activation

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(29), P. 15906 - 15911

Published: July 13, 2023

Desymmetrization is an essential method for the synthesis of chiral compounds, particularly biaryls. We have developed enantioselective axially biaryls by desymmetrization using C(sp3)-H activation catalyzed palladium phosphate. Mechanistic studies show that C-H rate- and enantiomer-determining step. To best our knowledge, this first report asymmetric compounds activation.

Language: Английский

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Kinetic resolution of substituted amido[2.2]paracyclophanes via asymmetric electrophilic amination

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

Published: Aug. 28, 2023

Planar chiral [2.2]paracyclophane derivatives are a type of structurally intriguing and practically useful molecules, which have found range important applications in the field asymmetric catalysis material science. However, access to enantioenriched [2.2]paracyclophanes represents longstanding challenge organic synthesis due their unique structures, still highly dependent on chromatography separation technique classical chemical resolution strategy date. In this work, we report an efficient versatile kinetic protocol for various substituted amido[2.2]paracyclophanes, including those with pseudo-geminal, pseudo-ortho, pseudo-meta pseudo-para disubstitutions, using phosphoric acid (CPA)-catalyzed amination reaction, was also applicable enantioselective desymmetrization achiral diamido[2.2]paracyclophane. Detailed experimental studies shed light new reaction mechanism electrophilic aromatic C-H amination, proceeded through sequential triazane formation N[1,5]-rearrangement. The facile large-scale diverse derivatizations both recovered starting materials products showcased potential method.

Language: Английский

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An overview of the applications of chiral phosphoric acid organocatalysts in enantioselective additions to CO and CN bonds

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(22), P. 6331 - 6399

Published: Jan. 1, 2022

Since 2004, chiral phosphoric acids (CPAs) have emerged as highyl efficient organocatalysts, providing excellent results in a wide reaction scope. In this review, the applications of CPA for enantioselective additions to CO and CN bonds are covered.

Language: Английский

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Epoxides: Small Rings to Play with under Asymmetric Organocatalysis

ACS Organic & Inorganic Au, Journal Year: 2022, Volume and Issue: 2(4), P. 289 - 305

Published: March 29, 2022

Optically pure epoxides are recognized as highly valuable products and key intermediates, useful in different areas from pharmaceutical agrochemical industries to natural product synthesis materials science. The predictable fate of the ring-opening process, terms stereoselectivity often regioselectivity, enables functional groups be installed at vicinal carbon atoms a desired manner. In this way, widespread utility either for synthetic applications or final can obtained. advent asymmetric organocatalysis provided new convenient tool, not only their preparation but also elaboration class heterocycles. review, we focus on recent developments stereoselective organocatalytic reactions meso-epoxides, kinetic resolution racemic epoxides, Meinwald-type rearrangement. Examples processes toward specific targets, which include ring opening an epoxide intermediate, illustrated.

Language: Английский

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Organocatalytic Dynamic Kinetic Resolution: An Update

European Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 2022(7)

Published: Feb. 17, 2022

Abstract It is only in the two last decades that first examples of organocatalytic dynamic kinetic resolutions (DKRs) have been disclosed. These methodologies allow resolving racemic compounds with up to quantitative yield. Today, a variety chiral organocatalysts are capable providing excellent enantioselectivities many types transformations evolving through DKR. The goal this review update field DKRs since 2016. divided into six sections, according different employed these reactions, such as Brønsted acid catalysts, hydrogen‐bonding N‐heterocyclic carbene Lewis base phase‐transfer and cinchona alkaloid‐based catalysts.

Language: Английский

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