High-order dipolar annulations with metal-containing reactive dipoles

Chemical Society Reviews, Год журнала: 2022, Номер 51(10), С. 4146 - 4174

Опубликована: Янв. 1, 2022

The advances on metal-catalysed high-order dipolar annulations were comprehensively summarized in this review. To further exploit the potential of unique annulation strategy, a research outlook was also proposed.

Язык: Английский

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Palladium-Catalyzed Ligand-Controlled Switchable Hetero-(5 + 3)/Enantioselective [2σ+2σ] Cycloadditions of Bicyclobutanes with Vinyl Oxiranes

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(29), С. 19621 - 19628

Опубликована: Май 13, 2024

For nearly 60 years, significant research efforts have been focused on developing strategies for the cycloaddition of bicyclobutanes (BCBs). However, higher-order and catalytic asymmetric BCBs long-standing formidable challenges. Here, we report Pd-catalyzed ligand-controlled, tunable cycloadditions divergent synthesis bridged bicyclic frameworks. The dppb ligand facilitates formal (5+3) vinyl oxiranes, yielding valuable eight-membered ethers with scaffolds in 100% regioselectivity. Cy-DPEphos promotes selective hetero-[2σ+2σ] to access pharmacologically important 2-oxabicyclo[3.1.1]heptane (O-BCHeps). Furthermore, corresponding O-BCHeps 94–99% ee has achieved using chiral (S)-DTBM-Segphos, representing first cross-dimerization two strained rings. obtained are promising bioisosteres ortho-substituted benzenes.

Язык: Английский

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[3+2] Cycloaddition of alkyl aldehydes and alkynes enabled by photoinduced hydrogen atom transfer

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Авг. 12, 2022

Abstract [3+2] Cycloaddition is a step- and atom-economic method for the synthesis of five-membered rings. Despite great success 1,3-dipolar cycloadditions, radical annulation alkynes remains formidable challenge. Herein, photoinduced decatungstate-catalyzed cycloaddition various internal using abundant aliphatic aldehydes as three-carbon synthon developed, producing elaborate cyclopentanones in 100% atom economy with excellent site-, regio-, diastereoselectivity under mild conditions. The catalytic cycle consists hydrogen abstraction from aldehydes, addition, 1,5-hydrogen transfer, anti-Baldwin 5-endo-trig cyclization, back abstraction. power this showcased by late-stage elaboration medicinally relevant molecules total or formal (±)-β-cuparenone, (±)-laurokamurene B, (±)-cuparene.

Язык: Английский

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Copper-catalysed convergent regio- and enantioselective alkynylallylic substitution

Nature Synthesis, Год журнала: 2022, Номер 2(1), С. 37 - 48

Опубликована: Окт. 24, 2022

Язык: Английский

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Recent advances of Pd-π-allyl zwitterions in cycloaddition reactions

Chinese Chemical Letters, Год журнала: 2023, Номер 34(11), С. 108401 - 108401

Опубликована: Март 30, 2023

Язык: Английский

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Sadphos as Adaptive Ligands in Asymmetric Palladium Catalysis

Accounts of Chemical Research, Год журнала: 2024, Номер unknown

Опубликована: Янв. 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.

Язык: Английский

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Divergent Enantioselective Access to Diverse Chiral Compounds from Bicyclo[1.1.0]butanes and α,β-Unsaturated Ketones under Catalyst Control

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Сен. 30, 2024

Achieving structural and stereogenic diversity from the same starting materials remains a fundamental challenge in organic synthesis, requiring precise control over selectivity. Here, we report divergent catalytic methods that selectively yield either cycloaddition or addition/elimination products bicyclo[1.1.0]butanes α,β-unsaturated ketones. By employing chiral Lewis acid Brønsted catalysts, achieved excellent regio-, diastereo-, enantioselectivity across all three distinct transformations, affording diverse array of synthetically valuable bicyclo[2.1.1]hexanes cyclobutenes. The outcomes are controlled by differential activation substrates specific catalyst with reaction conditions dictating pathway This strategy demonstrates power catalysis creating molecular complexity diversity, offering tool for synthesis enantioenriched building blocks.

Язык: Английский

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Asymmetric Auto‐Tandem Palladium Catalysis for 2,4‐Dienyl Carbonates: Ligand‐Controlled Divergent Synthesis

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(17)

Опубликована: Фев. 14, 2022

Developing new asymmetric auto-tandem catalysis processes, especially in a divergent manner, is highly attractive but extremely challenging. Presented herein palladium-catalyzed reaction between 2,4-dienyl carbonates and o-TsNH arylimines or trifluoroacetophenones that proceeds through consecutive N-allylation, vinylogous addition, π-σ-π isomerization, another N-allylation sequence. Importantly, switchable diastereodivergent synthesis could be achieved by tuning the chiral bisphosphine ligands, which led to construction of broad spectrum fused tetrahydroquinoline architectures with moderate excellent enantioselectivity. Ligand control even enabled effective access regiodivergent azetidine chemodivergent β-H elimination fair enantioselectivity, further showing versatility current catalysis.

Язык: Английский

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Palladium-Catalyzed Site-Selective Regiodivergent Carbocyclization of Di- and Trienallenes: A Switch between Substituted Cyclohexene and Cyclobutene

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 6, 2025

Nature efficiently produces a myriad of structurally diverse carbon ring frameworks from common linear precursors via cyclization reactions at specific olefinic sites in dienes or polyenes. In contrast, achieving the site-selective functionalization diene polyene substrates remains formidable challenge chemical synthesis. Herein, we report pair highly site-selective, regiodivergent carbocyclization dienallenes and trienallenes, enabling efficient synthesis cis-1,4-disubstituted cyclohexenes trans-1,2-disubstituted cyclobutenes precursor with high diastereoselectivity. Remarkably, simple achiral organophosphoric acids amines are identified as powerful ligands for controlling these palladium-catalyzed carbocyclizations. This approach represents first example carbocyclization, providing practical method stereospecific thermodynamically disfavored fully substituted trans-1,2-cyclobutenes. Additionally, methodology developed offers general insights into development metal-catalyzed carbocyclizations precursors, mimicking natural processes.

Язык: Английский

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Recent advances in ligand-enabled palladium-catalyzed divergent synthesis

Organic & Biomolecular Chemistry, Год журнала: 2023, Номер 22(1), С. 37 - 54

Опубликована: Ноя. 27, 2023

Developing efficient and straightforward strategies to rapidly construct structurally distinct diverse organic molecules is one of the most fundamental tasks in synthesis, drug discovery materials science. In recent years, divergent synthesis functional from same starting has attracted significant attention been recognized as an powerful strategy. To achieve this objective, proper adjustment reaction conditions, such catalysts, solvents, ligands, etc., required. review, we summarized efforts chemo-, regio- stereodivergent reactions involving acyclic cyclic systems catalyzed by palladium complexes. Meanwhile, types, including carbonylative reactions, coupling cycloaddition well probable mechanism have also highlighted detail.

Язык: Английский

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