Palladium(0) π-Lewis Base Catalysis: Concept and Development

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(10), С. 6422 - 6437

Опубликована: Март 1, 2024

The development of a new catalytic strategy plays vital role in modern organic chemistry since it permits bond formation an unprecedented and more efficient manner. Although the application preformed metal complexes as π-base-activated reagents have enabled diverse transformations elegantly, concept by directly utilizing transition metals π-Lewis base catalysts remain underdeveloped, especially field asymmetric catalysis. Here, we outline our perspective on discovery palladium(0) catalyst, which is capable increasing highest occupied molecular orbital (HOMO) energy both electron-neutral electron-deficient 1,3-dienes 1,3-enynes upon flexible η2-complexes formed situ resultant π-backdonation. Thus, fruitful carbon–carbon-forming reactions with electrophiles can be achieved enantioselectively vinylogous addition pattern, conceptually different from classical oxidative cyclization mechanism. Emphasis will given to mechanism elucidation, features, reaction design together further this emerging field.

Язык: Английский

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4-Vinylbenzodioxinones as a new type of precursor for palladium-catalyzed (4+3) cycloaddition of azomethine imines

Chemical Communications, Год журнала: 2024, Номер 60(11), С. 1436 - 1439

Опубликована: Янв. 1, 2024

Benzo-fused cyclic carbonates were designed and synthesized as a novel type of precursor π-allylpalladium zwitterionic intermediates.

Язык: Английский

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Base‐Mediated Four‐Component Intramolecular Cyclization reaction: One‐pot Access to Imidazole‐4‐(2H)‐ones

Advanced Synthesis & Catalysis, Год журнала: 2025, Номер unknown

Опубликована: Янв. 22, 2025

Abstract A base‐mediated one‐pot, two‐step, four‐component reaction has been developed to synthesize imidazole‐4(2 H )‐ones, utilizing commercially available amino acid esters, aldehydes, alkynes, and alcohols. Control experiments isolation of the intermediate revealed mechanistic details. This proceeds via imine formation, followed by nucleophilic addition alkyne form a propargylamine precursor. Subsequently, precursor under undergoes conversion into 1‐azadiene, in situ ketene formation generate (allylideneamino)prop‐1‐en‐1‐one. The alcohol subsequent intramolecular cyclization provides imidazole‐4 (2 )‐ones exclusively.

Язык: Английский

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Pd-catalyzed exclusively regioselective [5 + 4] cycloaddition for the construction of 1,5-di/ox-azonanes

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(7), С. 1680 - 1685

Опубликована: Янв. 1, 2023

An efficient approach for the exclusively regioselective construction of 1,5-di/ox-azonanes via Pd-catalyzed [5 + 4] cycloaddition has been developed.

Язык: Английский

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Cu-Catalyzed Divergent Transformations of Allenylethylene Carbonates with Diboron Reagents

Organic Letters, Год журнала: 2024, Номер 26(4), С. 960 - 965

Опубликована: Янв. 19, 2024

Divergent transformations of allenylethylene carbonates with diboron reagents catalyzed by copper are disclosed. By using CuCl/IPr·HCl as the catalyst, react B2hex2 to afford 2,4-dien-1-ols product in presence Cs2CO3 base, iPrOH additive, and 1,4-dioxane solvent. And they B2pin2 form boronic half acids NaOtBu water THF The reactions corresponding products good stereoselectivities yields, further derivatizations study mechanism also demonstrated.

Язык: Английский

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Facile Synthesis of Quinoline-Substituted 3-Hydroxy-2-oxindoles and 3-Amino-2-oxindoles via a Palladium-Catalyzed Cascade Intramolecular Cyclization/Intermolecular Nucleophilic Addition Reaction

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(5), С. 3413 - 3418

Опубликована: Фев. 20, 2024

An efficient cascade intramolecular cyclization/intermolecular nucleophilic addition reaction of allenyl benzoxazinone with isatin or isatin-derived ketimine has been established by using Pd0-π-Lewis base catalysis. A series 3-hydroxy-2-oxindoles and 3-amino-2-oxindoles quaternary carbon atoms at the C3 position were synthesized in good yields under mild conditions through this protocol.

Язык: Английский

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Palladium-catalyzed asymmetric [4 + 3] cycloaddition of methylene-trimethylenemethane: access to seven-membered exocyclic axially chiral allenes

Chemical Science, Год журнала: 2024, Номер 15(25), С. 9703 - 9708

Опубликована: Янв. 1, 2024

A palladium-catalyzed asymmetric [4 + 3] cycloaddition of the methylene-trimethylenemethane donor with an azadiene has been developed, affording benzofuro[3,2- b ]azepine-derived exocyclic chiral allene control axial and point chirality.

Язык: Английский

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Palladium-catalyzed [6 + 4] cycloaddition with π-allyl all-carbon 1,6-dipole for the synthesis of ten-membered heterocycles

Organic Chemistry Frontiers, Год журнала: 2023, Номер 11(5), С. 1299 - 1304

Опубликована: Дек. 25, 2023

This work introduces a novel α,α-diester-δ-vinylvalerolactone as dipolar precursor in palladium-catalyzed [6 + 4] cycloaddition reaction with azadienes, resulting the production of ten-membered heterocycles.

Язык: Английский

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Advancements in Asymmetric Catalytic Approaches Involving Benzoxazinone Derivatives

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(17), С. 2767 - 2788

Опубликована: Июль 10, 2023

Abstract Chiral aza ‐heterocycles, as a sort of key frameworks natural products et al , are deeply concerned by synthetic chemists. In recent years, catalytic asymmetric reactions several types zwitterionic intermediates, originating form benzoxazinone derivatives, have become popular and efficient approach to obtain chiral ‐heterocycles. Given that, this review attempts summarize development in the field derivatives powerful dipole precursors for construction past various their been developed. Herein, is organized display important potentials values.

Язык: Английский

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Asymmetric 2,4-Dienylation/[4 + 2] Annulation Cascade to Construct Fused Frameworks via Auto-Tandem Palladium Catalysis

Organic Letters, Год журнала: 2023, Номер 25(20), С. 3682 - 3686

Опубликована: Май 16, 2023

A palladium catalyzed tandem reaction between ortho-functionalized aryl enones and 2,4-dienyl carbonates has been presented, proceeding through sequential 2,4-dienylation/Michael addition/π-σ-π isomerization/allylic alkylation. broad array of enantioenriched architectures having fused spirocyclic frameworks are constructed in moderate to excellent yields stereoselectivity. Notably, the intrinsic intramolecular Diels-Alder pattern dienylated intermediates is well reversed via Pd(0)-π-Lewis base catalysis.

Язык: Английский

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