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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trans-Hydroalkynylation of Internal 1,3-Enynes Enabled by Cooperative Catalysis

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(10), С. 5624 - 5630

Опубликована: Март 2, 2023

A cooperative catalyst system involving a Pd(0)/Senphos complex, tris(pentafluorophenyl)borane, copper bromide, and an amine base, is demonstrated to catalyze trans-hydroalkynylation of internal 1,3-enynes. For the first time, Lewis acid shown promote reaction emerging outer-sphere oxidative step. The resulting cross-conjugated dieneynes are versatile synthons for organic synthesis, their characterization reveals distinct photophysical properties depending on positioning donor/acceptor substituents along conjugation path.

Язык: Английский

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Enantioselective Cross-[4 + 2]-Cycloaddition/Decarboxylation of 2-Pyrones by Cooperative Catalysis of the Pd(0)/NHC Complex and Chiral Phosphoric Acid

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(10), С. 6936 - 6946

Опубликована: Фев. 28, 2024

Here, we describe a cooperative Pd(0)/chiral phosphoric acid catalytic system that allows us to realize the first chemo-, regio-, and enantioselective sequential cross-[4 + 2]-cycloaddition/decarboxylation reaction between 2-pyrones unactivated acyclic 1,3-dienes. The key success of this transformation is utilization an achiral N-heterocyclic carbene (NHC) as ligand newly developed chiral cocatalyst. Experimental investigations computational studies support idea Pd(0)/NHC complex acts π-Lewis base increase nucleophilicity 1,3-dienes via η2 coordination, while simultaneously increases electrophilicity by hydrogen bonding. By synergistic catalysis, 2]-cycloaddition decarboxylation proceeds efficiently, enabling preparation wide range vinyl-substituted 1,3-cyclohexadienes in good yields enantioselectivities. synthetic utility demonstrated transformations product various valuable six-membered carbocycles.

Язык: Английский

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Borataalkenes, boraalkenes, and the η²-B,C coordination mode in coordination chemistry and catalysis

Chemical Society Reviews, Год журнала: 2024, Номер 53(4), С. 1915 - 1935

Опубликована: Янв. 1, 2024

This review summarizes the recent advances in synthesis of transition metal borataalkene and boraalkene complexes, η 2 -B,C coordination mode homogeneous catalysis.

Язык: Английский

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Synthesis of Allenes by Hydroalkylation of 1,3-Enynes with Ketones Enabled by Cooperative Catalysis

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(39), С. 21638 - 21645

Опубликована: Сен. 22, 2023

A method for the synthesis of allenes by addition ketones to 1,3-enynes cooperative Pd(0)Senphos/B(C6F5)3/NR3 catalysis is described. wide range aryl- and aliphatic undergo various in high yields at room temperature. Mechanistic investigations revealed a rate-determining outer-sphere proton transfer mechanism, which was corroborated DFT calculations.

Язык: Английский

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Reductive Inner-Sphere Electrosynthesis of Ammonia via a Nonelectrocatalytic Outer-Sphere Redox

Langmuir, Год журнала: 2024, Номер 40(37), С. 19458 - 19466

Опубликована: Сен. 3, 2024

Electrochemistry of outer-sphere redox molecules involves an essentially intact primary coordination sphere with minimal secondary adjustments, resulting in very fast electron transfer events even without a noble metal-based electrocatalyst. Departing from conventional electrocatalytic paradigms, we incorporate these reaction coordinate adjustments species to stimulate the electrocatalysis energetically challenging inner-sphere substrates. Through this approach, are able show intricate 8e

Язык: Английский

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Facile construction of benzofulvene frameworks via a palladium-catalysed three-component reaction

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

A palladium-catalysed three-component reaction between 1,3-enynes, 2-formylphenylboronic acids and N -sulfonyl amines has been developed, furnishing a variety of multifunctional benzofulvenes in moderate to good yields E / Z -selectivity.

Язык: Английский

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Substrate-controlled divergent synthesis withortho-vinyl-functionalised 1,3-enynes and iminesviapalladium catalysis

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(13), С. 3300 - 3306

Опубликована: Янв. 1, 2023

Substrate-controlled divergent cascade reactions between ortho -vinyl-functionalised 1,3-enynes and imines have been realised via palladium catalysis, furnishing collections of skeletally distinct architectures in good yields stereoselectivity.

Язык: Английский

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Rapid Construction of Hexahydro‐1H‐pyrrolo[3,2‐c]pyridines with Functionalized 1,3‐Enynes and Imines via Palladium Catalysis

Asian Journal of Organic Chemistry, Год журнала: 2023, Номер 12(6)

Опубликована: Май 18, 2023

Abstract Presented herein is a palladium catalyzed tandem reaction between 3‐aminoethyl group tethered 1,3‐enynes and imines, proceeding through cascade vinylogous addition/reductive elimination/protonation/allylic amination 1,3‐hydrogen transfer sequence. A collection of complex hexahydro‐1 H ‐pyrrolo[3,2‐ c ]pyridine architectures were straightforwardly constructed in moderate yields diastereoselectivity.

Язык: Английский

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Application of 1,4-Azaborines in Organic and Transition Metal Catalysis

Chinese Journal of Organic Chemistry, Год журнала: 2023, Номер 43(5), С. 1742 - 1742

Опубликована: Янв. 1, 2023

The recent progress of 1,4-azaborines in organic and transition metal catalysis is summarized, which consists three parts.The first part briefly describes the history 1,4-azaborines, second emphasizes on application as an organocatalyst aerobic photooxidation triaryl phosphines, last discribes use ligand palladium-catalyzed stereoselective borylation enynes.The future direction this field also proposed.

Язык: Английский

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