Electrochemical radical-polar crossover: a radical approach to polar chemistry

Science China Chemistry, Journal Year: 2023, Volume and Issue: 67(2), P. 450 - 470

Published: Nov. 3, 2023

Language: Английский

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

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 4395 - 4406

Published: March 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.

Language: Английский

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

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(22), P. 15453 - 15463

Published: May 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.

Language: Английский

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Nickel/Quinim Enabled Asymmetric Carbamoyl‐Acylation of Unactivated Alkenes

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 41(14), P. 1673 - 1678

Published: Feb. 14, 2023

Comprehensive Summary Transition metal‐catalyzed difunctionalization of tethered alkene has emerged as a prevailing tool for the expedient construction synthetically valuable cyclic compounds. However, most efforts have been devoted to reaction styrene‐type substrates due their rigid scaffold and high reactivity. With respect nonaromatic olefin, especially mono‐substituted alkene, still remains largely underdeveloped. Herein, we disclose nickel/Quinim complex TBADT‐cocatalyzed asymmetric carbamoyl‐acylation unactivated on carbamoyl chlorides with diverse aldehydes. The exhibits broad substrate scope good functional group tolerance, well efficiency enantioselectivity. Both monosubstituted 1,1‐substituted alkenes can work either aliphatic or aromatic aldehydes under current protocol, providing convenient access an array medicinally useful chiral γ‐lactams derivatives bearing convertible acyl functionality. This showcases more application possibilities Quinim ligand in future catalytic transformations.

Language: Английский

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Palladium-Catalyzed Enantioselective Multicomponent Cross-Coupling of Trisubstituted Olefins

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(24), P. 16892 - 16901

Published: June 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.

Language: Английский

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Recent advances in dual photoredox/nickel catalyzed alkene carbofunctionalised reactions

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(68), P. 8946 - 8977

Published: Jan. 1, 2024

Alkene carbofunctionalization reactions have great potential for synthesizing complex molecules and constructing structures in natural products medicinal chemistry. Recently, dual photoredox/nickel catalysis has emerged as a novel strategy alkene carbofunctionalization. Nickel offers numerous advantages over other transition metals, such cost-effectiveness, abundance, low toxicity, moreover, it many oxidation states. catalysts exhibit excellent catalytic activity photoredox/transition metal catalysis, facilitating the formation of carbon-carbon or carbon-heteroatom bonds organic transformations. This review highlights latest advancements photoredox/nickel-catalyzed carbofunctionalizations includes literature published from 2020 to 2024.

Language: Английский

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Metallaphotoredox-Catalyzed Three-Component Asymmetric Cross-Electrophile Coupling for Chiral Boronate Synthesis

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(20), P. 15790 - 15798

Published: Oct. 10, 2024

Here, we report a photoredox and nickel-catalyzed cross-electrophile coupling strategy for the asymmetric three-component 1,2-alkylarylation of vinyl boronates with (hetero)aryl bromides (2°, 3°)-alkyl redox-active esters in presence Hantzsch ester. With fluorinated pyridyl-substituted chiral biimidazoline ligand, this reaction enables straightforward access to wide variety synthetically valuable α-aryl from readily available starting materials. This features mild conditions, broad substrate generality, good functional group tolerance proceeds without using metal reductants or alkyl halides. Furthermore, alkenyl halides other electron-deficient alkenes such as acrylates phosphonates can be applied successfully. Preliminary mechanistic studies shed light on potential pathways roles organic amines.

Language: Английский

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Enantioselective Photoredox- and Cu-Catalyzed Cyanoalkylation of Styrenes via Deoxygenation of Alkoxyl Radicals with Organophosphorus Compounds(III)

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 11, 2025

The enantioselective cyanoalkylation of styrenes by a cooperative photoredox and copper catalysis system has been established, providing straightforward access to structurally diverse enantioenriched alkyl nitriles in good yields with excellent enantioselectivities under mild conditions via deoxygenation alkoxyl radicals organophosphorus compounds(III). In addition, the reaction features wide substrate scope functional group tolerance, resultant could be easily converted into series chiral carboxylic acids, amides, esters, etc.

Language: Английский

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Ni-catalyzed reductive alkylgermylation of activated alkenes: Modular access to polyfunctionalized alkyl germanes

Chem Catalysis, Journal Year: 2023, Volume and Issue: 3(12), P. 100819 - 100819

Published: Nov. 22, 2023

Language: Английский

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Iron-Catalyzed Regioselective Reductive Fluoroalkylalkenylation of Unactivated Alkenes

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(3), P. 1575 - 1583

Published: Jan. 16, 2024

The example of iron-catalyzed reductive fluoroalkylalkenylation unactivated alkenes has been disclosed, affording the stereodefined homoallylic fluoroalkanes with high efficiency and regioselectivity. This three-component cross-electrophile coupling features directing groups free, good functional group tolerance, broad substrate scope, late-stage difunctionalization biorelevant molecules. Moreover, this protocol sheds light on distinct reactivity disparities between fluoroalkyl nonfluoroalkyl radicals in cross-coupling reactions, highlighting unique nature iron/B2pin2 systems.

Language: Английский

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