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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Catalytic asymmetric synthesis of silicon-stereogenic organosilanes

Chem, Journal Year: 2023, Volume and Issue: 9(12), P. 3461 - 3514

Published: Oct. 19, 2023

Language: Английский

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Organocatalytic enantioselective construction of Si-stereocenters: recent advances and perspectives

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(17), P. 8546 - 8562

Published: Jan. 1, 2024

Silicon-stereogenic chiral organosilanes have found increasing applications in synthetic chemistry, medicinal and materials science. In this context, various asymmetric catalytic methods been established for the diverse synthesis of silicon-stereogenic silanes. particular, organocatalysis is emerging as an important complementary tool enantioselective construction silicon-stereocenters, along with rapid development chiral-metal catalyzed protocols. Its advent provides a powerful platform to achieve functionalized structural diversity, should lead great organosilicon chemistry. Tutorial Review, we highlight these latest achievements from two aspects: desymmetrizations prochiral tetraorganosilanes dynamic kinetic transformations racemic by employing five organocatalytic activation modes. The advantages, limitations value each protocol, well opportunities still open further exploration, are also discussed.

Language: Английский

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Catalytic Enantioselective Aminative Difunctionalization of Alkenes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(10), P. 7029 - 7038

Published: March 1, 2024

Enantioselective difunctionalization of alkenes offers a straightforward means for the rapid construction enantioenriched complex molecules. Despite tremendous efforts devoted to this field, enantioselective aminative remains challenge, particularly through an electrophilic addition fashion. Herein, we report unprecedented approach via copper-catalyzed with external azo compounds as nitrogen sources. A series valuable cyclic hydrazine derivatives either [3 + 2] cycloaddition or intramolecular cyclization have been achieved in high chemo-, regio-, enantio-, and diastereoselectivities. In transformation, wide range functional groups, such carboxylic acid, hydroxy, amide, sulfonamide, aryl could serve nucleophiles. Importantly, new cyano oxazoline chiral ligand was found play crucial role control enantioselectivity.

Language: Английский

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Chemodivergent and Enantioselective Synthesis of Spirobi[dihydrophenalene] Structures

Organic Letters, Journal Year: 2025, Volume and Issue: 27(3), P. 869 - 873

Published: Jan. 10, 2025

The development and enantioselective synthesis of two types C2-symmetric spirobi[dihydrophenalene] structures is reported. reaction proceeds via rhodium-catalyzed 2-fold asymmetric conjugate arylation dienones followed by BF3·OEt2-promoted spirocyclization to give the enantiopure spiro products. Additive-dependent chemodivergent 3,3'-diarylated 2,2',3,3'-tetrahydro-1,1'-spirobi[phenalene]-9,9'-diols (3,3'-Ar2-SPHENOLs) corresponding diary ethers from same intermediate achieved. structural properties 3,3'-Ph2-SPHENOL are analyzed, its application in catalysis has been preliminarily demonstrated.

Language: Английский

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Amino Acid-Derived Ionic Chiral Catalysts Enable Desymmetrizing Cross-Coupling to Remote Acyclic Quaternary Stereocenters

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(30), P. 16796 - 16811

Published: July 20, 2023

Synthetic application of asymmetric catalysis relies on strategic alignment bond construction to creation chirality a target molecule. Remote desymmetrization offers distinctive advantages spatial decoupling catalytic transformation and generation stereogenic element. However, such separation presents substantial difficulties for the chiral catalyst discriminate distant enantiotopic sites through reaction three or more bonds away from prochirality center. Here, we report strategy that establishes acyclic quaternary carbon stereocenters cross-coupling reactions at distal positions aryl substituents. The new class amino acid-derived ionic catalysts enables desymmetrizing (enantiotopic-group-selective) Suzuki-Miyaura reaction, Sonogashira Buchwald-Hartwig amination between diverse diarylmethane scaffolds aryl, alkynyl, coupling partners, providing rapid access enantioenriched molecules project substituents widely spaced in three-dimensional space. Experimental computational investigations reveal electrostatic steering substrates by C-terminus ligands interactions. Cooperative ion-dipole interactions catalyst's amide group potassium cation aid preorganization transmits asymmetry product. This study demonstrates it is practical achieve precise long-range stereocontrol engineering arrangements catalysts' substrate-recognizing groups metal centers.

Language: Английский

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Asymmetric synthesis of saddle-shaped eight-membered azaheterocycles via (dynamic) kinetic resolution

Chem Catalysis, Journal Year: 2023, Volume and Issue: 4(1), P. 100827 - 100827

Published: Dec. 4, 2023

Language: Английский

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Enantioselective Copper‐Catalyzed Sequential Hydrosilylation of Arylmethylenecyclopropanes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: July 18, 2024

Abstract Despite impressive advances in the construction of enantioenriched silacarbocycles featuring silicon‐stereogenic centers via a selection well‐defined sila‐synthons, development more convenient and economic method with readily available starting materials is significantly less explored remains considerable challenge. Herein, we report first example copper‐catalyzed sequential hydrosilylation accessible methylenecyclopropanes (MCPs) primary silanes, affording an efficient route to wide range chiral silacyclopentanes bearing consecutive silicon‐ carbon‐stereogenic excellent enantio‐ diastereoselectivities (generally ≥98 % ee, >25 : 1 dr). Mechanistic studies reveal that these reactions combine intermolecular ring‐opening aryl MCPs intramolecular asymmetric resultant Z / E mixture homoallylic silanes.

Language: Английский

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Cocatalyst-Dependent Divergent Amination of Alkylgold Intermediates with Azodicarboxylates

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 5211 - 5218

Published: March 12, 2025

The asymmetric electrophilic amination using azodicarboxylates as the N-source for construction of C–N bond has attracted much attention over past decades. However, use in situ formed nucleophilic intermediates, rather than bench-stable reagents, remains elusive and challenging. Herein, we disclose an enantioselective reaction generated alkylgold species with under a gold complex chiral quinine-derived squaramide (QN-SQA) synergetic catalysis, leading to alkylideneoxazolines nitrogen-containing tertiary carbon stereocenter good high yields enantioselectivities. Moreover, starting from same oxazoles incorporating aminomethyl group on 5-position could be obtained by Brønsted acid relay catalysis via alkylideneoxazoline species. This method offers complementary approach through interception With this strategic protocol, further synthetic applications can envisioned catalytic C–C C–X bonds.

Language: Английский

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Controlling Stereoselectivity with Noncovalent Interactions in Chiral Phosphoric Acid Organocatalysis

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: March 18, 2025

Chiral phosphoric acids (CPAs) have emerged as highly effective Brønsted acid catalysts in an expanding range of asymmetric transformations, often through novel multifunctional substrate activation modes. Versatile and broadly appealing, these benefit from modular tunable structures, compatibility with additives. Given the unique types noncovalent interactions (NCIs) that can be established between CPAs various reactants─such hydrogen bonding, aromatic interactions, van der Waals forces─it is unsurprising catalyst systems become a promising approach for accessing diverse chiral product outcomes. This review aims to provide in-depth exploration mechanisms by which impart stereoselectivity, positioning NCIs central feature connects broad spectrum catalytic reactions. Spanning literature 2004 2024, it covers nucleophilic additions, radical atroposelective bond formations, highlighting applicability CPA organocatalysis. Special emphasis placed on structural mechanistic features govern CPA-substrate well tools techniques developed enhance our understanding their behavior. In addition emphasizing details stereocontrolling elements individual reactions, we carefully structured this natural progression specifics broader, class-level perspective. Overall, findings underscore critical role catalysis significant contributions advancing synthesis.

Language: Английский

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