Enantioselective Reductive Cross-Couplings of Olefins by Merging Electrochemistry with Nickel Catalysis

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(44), С. 23910 - 23917

Опубликована: Окт. 26, 2023

The merger of electrochemistry and transition metal catalysis has emerged as a powerful tool to join two electrophiles in an enantioselective manner. However, the development electroreductive cross-couplings olefins remains challenge. Inspired by advantages synergistic use with nickel catalysis, we present here Ni-catalyzed cross-coupling acrylates aryl halides alkyl bromides, which affords chiral α-aryl carbonyls good excellent enantioselectivity. Additionally, this catalytic reaction can be applied (hetero)aryl chlorides, is difficult achieve other methods. combination cyclic voltammetry analysis electrode potential studies suggests that NiI species activates oxidative addition bromides single-electron transfer.

Язык: Английский

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Enantioselective Directed Nickel-Catalyzed Three-Component Reductive Arylalkylation of Alkenes via the Carbometalation/Radical Cross-Coupling Sequence

ACS Catalysis, Год журнала: 2024, Номер 14(7), С. 4395 - 4406

Опубликована: Март 8, 2024

Asymmetric reductive three-component arylalkylation of alkenes via the radical relay method has been well established, while asymmetric migratory insertion strategy remains unexplored. We report enantioselective nickel-catalyzed cross-electrophile with aryl- and alkyl halides an integrated Heck carbometalation/radical cross-coupling sequence. This protocol employing a chiral Ni/PHOX catalytic system allows terminal internal to successfully engage exquisite control regio-, chemo-, stereoselectivity. More importantly, this undergoes regio- arylnickelation followed by Csp3–Csp3 elimination, thus exhibiting reverse regioselectivity method. Mild reaction conditions exceptional functional group tolerance facilitate method's compatibility bioactive motifs modular synthesis biologically active compounds. The experiments density theory calculations provide insights into mechanism origin stereoselectivity, hemilabile nature PHOX ligand is critical for achieving arylalkylation.

Язык: Английский

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Ligand-Controlled, Nickel-Catalyzed Stereodivergent Construction of 1,3-Nonadjacent Stereocenters

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(22), С. 15453 - 15463

Опубликована: Май 25, 2024

In contrast to the asymmetric synthesis of molecules with a single stereocenter or 1,2-adjacent stereocenters, simultaneous construction acyclic 1,3-nonadjacent stereocenters via catalyst in an enantioselective and diastereoselective manner remains formidable challenge. Here, we demonstrate diastereodivergent through Ni-catalyzed reductive cyclization/cross-coupling alkene-tethered aryl bromides α-bromoamides, which represents major remaining stereochemical challenge cyclization/difunctionalization alkenes. Using Ming-Phos as ligand, diverse set oxindoles containing were obtained high levels enantio- diastereoselectivity. Mechanistic experiments density functional theory calculations indicate that magnesium salt plays key role controlling Furthermore, another complementary stereoisomeric products constructed from same starting materials using Ph-Phox ligand.

Язык: Английский

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Benzophenothiazine/Boronic Acid Cooperative Photocatalysis Enables the Synthesis of γ-Lactones via the [3 + 2] Cycloaddition of α,β-Unsaturated Carboxylic Acids with Olefins

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4975 - 4983

Опубликована: Март 10, 2025

Язык: Английский

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Palladium-Catalyzed Enantioselective Multicomponent Cross-Coupling of Trisubstituted Olefins

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(24), С. 16892 - 16901

Опубликована: Июнь 6, 2024

The development of a catalytic method for stereogenic carbon center formation holds immense significance in organic synthesis. Transition-metal-catalyzed cross-coupling reaction has been regarded as straightforward and efficient tool stereoselectively forging C–C bond. Nevertheless, the creation acyclic all-carbon quaternary-containing vicinal stereocenters remains notoriously challenging within domain chemistry despite their prominence various bioactive small molecules. Herein, we describe palladium-catalyzed asymmetric multicomponent trisubstituted alkene with aryl diazonium salts arylboronic acids to realize tertiary-quaternary centers high regio-, distereo-, enantioselectivity. Specifically, precise manipulation stereoconfiguration alkenes enables divergent stereoselective reaction, thus allowing facile construction all four enantiomers. Harnessing ligand-swap strategy involving chiral bisoxazoline an achiral fumarate individually accelerates enantioselective migratory insertion reductive elimination step process, supported by density functional theory (DFT) calculations, obviating requirement neighboring directing group internal olefin skeleton.

Язык: Английский

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Three-component dicarbofunctionalization of allylamines via nucleopalladation pathway: unlocking vicinal and geminal selectivity

Chemical Science, Год журнала: 2024, Номер 15(13), С. 4890 - 4896

Опубликована: Янв. 1, 2024

A palladium( ii )-catalyzed vicinal and geminal selective dicarbofunctionalization of allylamine embedded in a removable picolinamide auxiliary is developed by exploiting nucleopalladation-triggered intermolecular three-component coupling reaction.

Язык: Английский

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Enantioselective Synthesis of P-Chiral Phosphine Oxides Bearing an All-Carbon Quaternary Stereogenic Center via Palladium-Catalyzed Domino Heck–Suzuki Reaction

ACS Catalysis, Год журнала: 2024, Номер unknown, С. 14762 - 14768

Опубликована: Сен. 20, 2024

Язык: Английский

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Ligand-enabled Ni-catalysed dicarbofunctionalisation of alkenes with diverse native functional groups

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Ноя. 28, 2024

The transition metal-catalysed dicarbofunctionalisation of unactivated alkenes normally requires exogenous strong coordinated directing groups, thus reducing the overall reaction efficiency. Here, we report a ligand-enabled Ni(II)-catalysed with aryl/alkenyl boronic acids and alkyl halides as coupling partners diverse range native functional groups group. This protocol provides an efficient direct route towards vicinal 1,2-disubstituted alkanes using primary, secondary, tertiary amides, sulfonamides, well secondary amines under redox-neutral conditions that are challenging to access through conventional methods. key success this is use bulky β-diketone ligand, which could enable insertion alkene aryl-Ni(II) species, stabilize alkyl-Ni(II) species inhibit homolytic cleavage, supporting by both experimental computational studies. features group, broad substrate scope, excellent scalability. groups. authors

Язык: Английский

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Pd/Cu-Cocatalyzed Enantio- and Diastereodivergent Wacker-Type Dicarbofunctionalization of Unactivated Alkenes

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(38), С. 26121 - 26130

Опубликована: Авг. 5, 2024

The Wacker and Wacker-type reactions are some of the most fundamental powerful transformations in organic chemistry for their ability to efficiently produce valuable chemicals. Remarkable progress has been achieved asymmetric oxy/aza-Wacker-type reactions; however, dicarbofunctionalization remains underdeveloped, especially concurrent construction two stereocenters. Herein, we report a Pd/Cu-cocatalyzed enantio- diastereodivergent alkene-tethered aryl triflates with imino esters. A series 2-indanyl motifs bearing adjacent carbon stereocenters could be easily synthesized moderate excellent yields good diastereo- enantioselectivities (up >20:1 dr >99% ee). Density functional theory calculations revealed that origin diastereoselectivity this Pd/Cu synergistic catalytic system is jointly determined by both intermolecular anti-carbopalladation alkenes reductive elimination processes, accordance Curtin–Hammett principle.

Язык: Английский

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

Advanced Science, Год журнала: 2024, Номер unknown

Опубликована: Июль 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.

Язык: Английский

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