Catalytic Enantioselective Macrocyclization for the Synthesis of Planar‐Chiral Cyclophanes: Recent Updates

European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(47)

Опубликована: Авг. 28, 2024

Abstract The planar chirality of macrocycles is a fascinating research topic. Locking the configurational flip between benzene ring and macrocycle leads to chirality, which can significantly enhance biological activity cyclophanes. Planar‐chiral cyclophanes are widely used in pharmaceuticals, chiral catalysts, functional materials. However, accessing planar‐chiral via asymmetric catalysis has remained challenging. Among various strategies, macrocyclization provides powerful tool for This method allows control when constructing greatly improves efficiency. There three types reactions: transition metal‐catalyzed, organocatalyzed, biocatalyzed. In addition, confinement strategy breaks through conservative synthetic approaches. review summarizes these achievements, aiming highlight catalytic synthesis inspire interested researchers.

Язык: Английский

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Central-to-Axial Chirality: Asymmetric Organocatalytic Synthesis of Axially Chiral Chalcones via Exocyclic Dihydronaphthalenes

Organic Letters, Год журнала: 2023, Номер 25(26), С. 4813 - 4818

Опубликована: Июнь 26, 2023

Asymmetric synthesis of an unprecedented exocyclic dihydronaphthalene and axially chiral naphthalene chalcone has been disclosed. Good to excellent asymmetric induction is achieved. The success attributed the unusual formation dihydronaphthalene, which plays a crucial role in ensuring axial chirality. This first report molecules capable enabling chalcones via stepwise vinylogous domino double-isomerization using secondary amine catalysis.

Язык: Английский

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Chiral α-Aminophosphonates as Ligands in Copper-Catalyzed Asymmetric Oxidative Coupling of 2-Naphthols

Organic Letters, Год журнала: 2024, Номер 26(25), С. 5274 - 5279

Опубликована: Июнь 17, 2024

Chiral α-aminophosphonates with adjacent carbon and phosphonate stereogenic centers have been employed as ligands in the copper-catalyzed oxidative coupling of 2-naphthols, resulting production chiral BINOLs favorable yields moderate to good enantiomeric excess. This represents first application P-based enable such a transformation. The synthesis these α-aminophosphonate offers significant advantage over approaches that typically necessitate elaborate synthetic processes for ligand production.

Язык: Английский

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Conformationally Defined Planar-Chiral [n]Paracyclophanes Stabilized by Chiral Ansa Chains

Research Square (Research Square), Год журнала: 2025, Номер unknown

Опубликована: Янв. 6, 2025

Although chiral substituents have been incorporated into ansa chains to stabilize the conformations of cyclophanes and modulate the biological activities pharmaceuticals, asymmetric syntheses these atropisomers relies on substrate-induced diastereoselective macrocyclization. Consequently, enantio-, atrop-, macrocyclizations are yet be reported. Herein, we describe a N-heterocyclic carbene (NHC) phosphoric acid (CPA) dual-catalytic process for desymmetrization 1,3-diols, achieve macrocyclization stereoselective control over two elements. It was deduced that hydrogen bonding CPA with 1,3-diols enhanced diastereoselectivity process. As result, various planar-chiral bearing were synthesized. Thermodynamic experiments revealed presence an all-carbon quaternary carbon center chain significantly increased rotational barriers cyclophanes. Moreover, density functional theory calculations suggested substituent shrinks by compressing bond angle, thereby rendering conformational rotation reaction more challenging.

Язык: 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, Год журнала: 2025, Номер unknown

Опубликована: Март 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.

Язык: Английский

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Enantio-, atrop-, and diastereoselective macrolactonization to access type III cyclophanes

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Апрель 3, 2025

Язык: Английский

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Visible Light-Driven Construction of Axially Chiral Heterocyclic Compounds

Topics in heterocyclic chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Язык: Английский

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Atroposelective synthesis of eight-membered lactam-bridged N-arylindoles via stepwise cut-and-sew strategy

Cell Reports Physical Science, Год журнала: 2023, Номер 4(12), С. 101697 - 101697

Опубликована: Ноя. 22, 2023

The development of efficient processes for the preparation structurally diverse axially chiral biaryls has been an important goal in synthetic organic chemistry and asymmetric catalysis. However, sharp contrast to well-established open-chain biaryls, catalytic enantioselective construction medium-sized bridged remains underdeveloped. In particular, no synthesis such frameworks possessing a configurationally stable stereogenic C-N axis with step- or pot-economy disclosed. Herein, we report practical atropisomeric eight-membered lactam-bridged N-arylindoles through conceptually intriguing stepwise cut-and-sew strategy. key success lies silver-catalyzed atroposelective ring-opening/cyclization cascade reaction N-arylindole lactams isocyanoacetates establish axial chirality. This method features operational simplicity, good functional group tolerance, high efficiency, as well enantiocontrol. It is also noteworthy that these scaffolds exhibit large Stokes shifts, demonstrating their potential applications fluorescent dyes.

Язык: Английский

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Catalytic Atroposelective Synthesis of Axially Chiral Azomethine Imines and Neuroprotective Activity Evaluation

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(5)

Опубликована: Ноя. 30, 2023

Azomethine imines, as a prominent class of 1,3-dipolar species, hold great significance and potential in organic medicinal chemistry. However, the reported synthesis centrally chiral azomethine imines relies on kinetic resolution, construction axially remains unexplored. Herein, we present through copper- or phosphoric acid catalyzed ring-closure reactions N'-(2-alkynylbenzylidene)hydrazides, showcasing high efficiency, mild conditions, broad substrate scope, excellent enantioselectivity. Furthermore, biological evaluation revealed that synthesized effectively protect dorsal root ganglia (DRG) neurons by inhibiting apoptosis induced oxaliplatin, offering promising therapeutic approach for chemotherapy-induced peripheral neuropathy (CIPN). Remarkably, (S)- (R)-atropisomers displayed distinct neuroprotective activities, underscoring axial stereochemistry.

Язык: Английский

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Metal‐Catalyzed Enantioselective Cleavage of Aromatic C−O Bonds

ChemCatChem, Год журнала: 2024, Номер 16(12)

Опубликована: Апрель 18, 2024

Abstract Phenol derivatives are naturally abundant or can be easily fabricated from commercially accessible building blocks. In recent years, with the aim of producing functionally important chiral compounds in enantioenriched form, there has been initial progress development metal‐catalyzed cross‐coupling reactions that involve enantioselective cleavage aromatic C−O bonds. This concept encompasses a review significant advancements this field, as well associated strategies. Moreover, challenges and potential opportunities area also underscored.

Язык: Английский

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