Beyond conventional: Role of chiral metal–organic frameworks in asymmetric scenarios

Nano Today, Journal Year: 2024, Volume and Issue: 56, P. 102227 - 102227

Published: March 18, 2024

Language: Английский

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Sadphos as Adaptive Ligands in Asymmetric Palladium Catalysis

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 31, 2024

ConspectusPalladium catalysis, as one of the most important strategies in asymmetric synthesis, has continuously attracted attention organic chemists. With development chiral ligands, increasingly challenging reactions and substantial progress catalysis are being realized.Since 2014, we have focused on exploiting a series sulfinamide phosphine ligands called "Sadphos," including Ming-Phos, Xu-Phos, Xiao-Phos, Xiang-Phos, TY-Phos, PC-Phos, GF-Phos, WJ-Phos. These can be easily prepared two to four steps using commercial materials. new types shown remarkable performance transition-metal-catalyzed reactions, especially Pd-catalyzed transformations. X-ray diffraction analysis, mechanistic studies, density functional theory calculations revealed that Sadphos coordinate with Pd0 PdII species Pd0/P, Pd0/P,S, or PdII/P,O modes.This Account summarizes our recent efforts toward palladium-catalyzed enantioselective ligands. were found privileged very crucial promote by increasing reactivity enantioselectivity. Ming-Phos is an effective ligand coupling intramolecular Heck providing highly trisubstituted allenes, axially anilides, gem-diarylmethine silanes, disubstituted dihydroisoquinolinones. Incorporation electron-rich cyclohexyl group moiety afforded which showed unique effect transformations, reductive Heck, dearomative Mizoroki–Heck, tandem Heck/Suzuki coupling, carboiodination, carboamination, cross-coupling reactions. Using similar strategy, synthesized more electron–rich TY-Phos Xiang-Phos bearing t-butyl 1-adamantyl at P atoms, respectively. Regarding stereoelectronic features, these characteristic best choice satisfy requirements fluoroarylation gem-difluoroalkenes, intermolecular α-arylation aldehydes, carboetherification alkenyl oximes, carboheterofunctionalization 2,3-dihydrofurans. Compared aforementioned attractive features high nucleophilicity originating from CH2PPh2 ortho-substituent side aryl ring, presumably responsible for its efficiency. The Pd/Xiao-Phos catalyst system shows good secondary oxides, affording P-stereogenic products multiple molecular skeletons. modification basic backbone introducing xanthene skeleton motivated us design synthesize monophosphines, named PC-Phos GF-Phos. various arylation sulfenate anions, denitrogenative cyclization benzotriazoles, dearomatization indoles. practicability GF-Phos was validated three-component N-tosylhydrazones, halides, terminal alkynes, well N-tosylhydrazones vinyl iodides pendent amines. In addition, ferrocene-derived WJ-Phos employed Suzuki–Miyaura reaction, biaryl monophosphine oxides excellent enantiomeric excesses.

Language: Английский

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Enantioselective construction of inherently chiral pillar[5]arenes via palladium-catalysed Suzuki–Miyaura cross-coupling

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: March 10, 2025

Pillar[n]arenes have broad applications in biological medicine, materials science, and supramolecular gels. Notably, enantiopure pillar[5]arenes are valued for their roles enantioselective host–guest recognition, chiral sensing, asymmetric catalysis, related fields. Current methods obtaining pillar[n]arenes rely heavily on resolution agents or HPLC resolution. However, the synthesis of these compounds via catalysis remains challenging. In this study, we develop an extended side-arm Suzuki–Miyaura cross-coupling strategy to construct inherently with excellent yields high enantioselectivities using a palladium catalyst Sadphos ligand. The reaction scope extends beyond arylboronic acids encompass 2-arylvinylboronic other multi-OTf-substituted substrates, all efficiently producing desired products. Further exploration synthetic applications, along photophysical chiroptical analyses, confirm potential diverse across multiple disciplines. Enantiopure recognition but current Here, authors pillar[5]arenes.

Language: Английский

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Ionic Hydrogen Bond‐Assisted Catalytic Construction of Nitrogen Stereogenic Center via Formal Desymmetrization of Remote Diols

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(31)

Published: May 15, 2024

The control of noncarbon stereogenic centers is profound importance owing to their enormous interest in bioactive compounds and chiral catalyst or ligand design for enantioselective synthesis. Despite various elegant approaches have been achieved construction S-, P-, Si- B-stereocenters over the past decades, catalyst-controlled strategies govern formation N-stereogenic garnered less attention. Here, we disclose first organocatalytic approach efficient access a wide range nitrogen-stereogenic through desymmetrization approach. Intriguingly, pro-chiral remote diols, which are previously not well addressed with enantiocontrol, differentiated by potent carbene-bound acyl azolium intermediates. Preliminary studies shed insights on critical ionic hydrogen bond (IHB) formed between dimer aggregate diols afford N-oxide products that feature tetrahedral nitrogen as sole element good yields excellent enantioselectivities. Notably, could offer an attractive strategy discovery potential antibacterial agrochemicals.

Language: Английский

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Application of Asymmetric Catalysis in Chiral Pesticide Active Molecule Synthesis

Journal of Agricultural and Food Chemistry, Journal Year: 2024, Volume and Issue: 72(31), P. 17153 - 17165

Published: July 25, 2024

The different configurations of chiral pesticides generally have significant influence on their biological activities. Chiral agrochemicals with high optical purities become a prominent topic in the research field new due to advantages including lower toxicity, higher efficiency, and reduced residue levels. However, most commercially available that possess elements are still used racemic forms. To date, asymmetric catalysis has emerged as versatile tool for enantioselective synthesis various novel pesticide active molecules. This perspective provides comprehensive overview applications diverse catalytic approaches facile preparation numerous molecules, our own outlook future development this highly direction is also presented at end review.

Language: Английский

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Enantioselective Aminosilylation of Alkenes by Palladium/Ming‐Phos‐Catalyzed Tandem Narasaka–Heck/Silylation Reaction

Advanced Science, Journal Year: 2024, Volume and Issue: unknown

Published: July 5, 2024

A Pd-catalyzed enantioselective aminosilylation of alkenes via tandem Aza-Heck/silylation reaction under Pd/Sadphos catalysis is disclosed. wide array oxime esters and silicon reagents are tolerated, furnishing the chiral pyrrolines bearing one quaternary or two contiguous stereocenters in good yield with high enantioselectivity. Not only terminal but also tri-substituented internal successfully participate reaction, delivering vicinal complete diastereoselectivity DFT study conducted to probe pathway origin enantioselectivity, which revealed that stereoinduction arises from weak interaction between aromatic ring substrate fragment naphthyl group ligand.

Language: Английский

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Rapid construction of a diterpene-inspired tetracyclic skeleton bearing bicyclo[3.2.1]octane rings based on desymmetrization of 1,3-diketones

Tetrahedron Letters, Journal Year: 2025, Volume and Issue: unknown, P. 155470 - 155470

Published: Jan. 1, 2025

Language: Английский

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SadPhos Library: A Comprehensive Resource for Exploring Chiral Ligand Chemical Space

Chemistry - An Asian Journal, Journal Year: 2025, Volume and Issue: unknown

Published: April 22, 2025

Abstract Traditionally, the discovery of ligands for organic reactions has relied heavily on intuition and experience chemists, leading to a trial‐and‐error process that is both time‐consuming inherently biased. The rise data science now offers more systematic efficient approach exploring chemical spaces, moving beyond heuristic constraints conventional ligand design enabling data‐driven, predictive method. In this study, we introduce “SadPhos Library”, comprehensive collection 890 reported chiral sulfinamide phosphine ligands, use physical descriptors systematically map their space. By examining small dataset known active demonstrate how SadPhos library can help identify key properties associated with performance thus streamline optimization. Furthermore, employing dimensionality reduction clustering techniques, pinpoint representative subset facilitates targeted exploration diverse landscape.

Language: Английский

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Immobilizing Stereogenic Nitrogen Center in Doubly Fused Triarylamines through Palladium-Catalyzed Asymmetric C–H Activation/Seven-Membered-Ring Formation

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(14), P. 9688 - 9694

Published: July 10, 2023

A series of doubly fused triarylamines containing conformationally stable stereogenic nitrogen centers has been constructed through palladium-catalyzed enantioselective C–H activation and imidoylative cyclization. The cyclization strategy forming an uncommon seven-membered heterocyclic ring employs readily available functionalized isocyanides aryl iodides as coupling partners under mild conditions. These helically twisted N-chiral frameworks contain no inner helical substituents or other chiral factors that stabilize the pyramidal conformation at nitrogen.

Language: Английский

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Enantiopurification by Co-Crystallization within Cyclodextrin Metal–Organic Framework

Crystals, Journal Year: 2024, Volume and Issue: 14(6), P. 568 - 568

Published: June 19, 2024

Tröger’s base analogs (TBAs) and their derivatives are versatile, Λ-shaped, tetracyclic chiral building blocks utilized in numerous fields of research. Although various methods for the enantiopurification TBAs have been demonstrated literature, none has achieved it with use metal–organic frameworks (MOFs). This investigation introduces a convenient scalable method to obtain enantiopure formation digestion MOF composed fully recoverable non-hazardous starting materials, namely, cyclodextrin-based framework (CD-MOF).

Language: Английский

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