Unlocking the Chain‐Walking Process in Gold Catalysis**

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(46)

Published: Oct. 2, 2023

The successful realization of gold-catalyzed chain-walking reactions, facilitated by ligand-enabled Au(I)/Au(III) redox catalysis, has been reported for the first time. This breakthrough led to development annulation reaction alkenes with iodoarenes leveraging interplay and π-activation reactivity mode. mechanism elucidated through comprehensive experimental computational studies.

Language: Английский

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Palladium Catalysis Enabled Sequential C(sp³)–H/C–C Activation: Access to Vinyl γ-Lactams

Organic Letters, Journal Year: 2024, Volume and Issue: 26(18), P. 3722 - 3726

Published: April 28, 2024

A Pd(II)-catalyzed tandem reaction of aliphatic amides with vinylcyclopropanes (VCPs) was accomplished by merging C(sp3)–H and C–C activation. The VCP revealed alkenylation/cyclization, followed ring opening via cleavage, delivering vinyl γ-lactams (E)-selectivity. role ligands, site-selectivity, functional group diversity, mechanistic insight, synthetic utilities are important practical features.

Language: Английский

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Ligand‐Enabled Ni^II‐Catalyzed Hydroxylarylation of Alkenes with Molecular Oxygen

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(35)

Published: July 11, 2023

The use of molecular oxygen as the terminal oxidant in transition metal catalyzed oxidative process is an appealing and challenging task organic synthetic chemistry. Here, we report a Ni-catalyzed hydroxylarylation unactivated alkenes enabled by β-diketone ligand with high efficiency excellent regioselectivity employing hydroxyl source. This reaction features mild conditions, broad substrate scope incredible heterocycle compatibility, providing variety β-hydroxylamides, γ-hydroxylamides, β-aminoalcohols, γ-aminoalcohols, 1,3-diols yields. value this methodology was demonstrated efficient synthesis two bioactive compounds, (±)-3'-methoxyl citreochlorol tea catechin metabolites M4.

Language: Английский

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Diphosphine Ligand‐Enabled Nickel‐Catalyzed Chelate‐Assisted Inner‐Selective Migratory Hydroarylation of Alkenes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(1)

Published: Nov. 21, 2023

The precise control of the regioselectivity in transition metal-catalyzed migratory hydrofunctionalization alkenes remains a big challenge. With transient ketimine directing group, nickel-catalyzed β-selective hydroarylation and hydroalkenylation alkenyl ketones has been realized with aryl boronic acids using alkyl halide as mild hydride source for first time. key to this success is use diphosphine ligand, which capable generation Ni(II)-H species presence bromide, enabling efficient insertion alkene into sequent rapid chain walking process. present approach diminishes organosilanes reductant, tolerates wide array complex functionalities excellent regioselective control. Moreover, catalytic system could also be applied azahetereoarenes, thus providing general preparation 1,2-aryl heteroaryl motifs potential applications pharmaceutical discovery.

Language: Английский

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Construction of Indole-Fused Seven- and Eight-Membered Azaheterocycles via a Tandem Pd/NBE-Catalyzed Decarbonylation and Dual C–H Activation Sequence

Organic Letters, Journal Year: 2023, Volume and Issue: 25(29), P. 5406 - 5410

Published: July 17, 2023

Herein, we report the transformation of aromatic acids to indole-fused seven- and eight-membered azaheterocycles. Two C-C bonds are formed via cleavage one bond two C-H bonds. The incorporation indole moieties into bioactive pharmaceuticals natural products construct a medium-sized polyfused heterocycle demonstrates synthetic utility protocol.

Language: Английский

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Direct Access to Quinone-Fused 5-Substituted-1,4-Benzodiazepine Scaffolds from Azidoquinones with/without [1,2]-Azide-Nitrogen Migration: Mechanistic Insights

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(23), P. 16315 - 16329

Published: Nov. 15, 2023

Seven-membered nitrogen heterocycles have a strong influence in drug discovery due to their inherent 3D character, which allows the ability explore vast conformational space with biological target. Notably, privileged 1,4-benzodiazepine scaffold is dominant treating central nervous system its binding affinity GABAA receptor. Herein, we report protocol for transformation of azidoquinones p-quinone fused 5-substituted-1,4-benzodiazepines (p-QBZDs) from InCl3-catalyzed intermolecular tandem cycloannulation amines and aldehydes. Detailed mechanistic studies reveal that EDA complex between InCl3 crucial determining reaction pathway. In absence formation, proceeds via intermediacy 2,3-bridged-2H-azirine followed by regiospecific addition an amine C═N/ring opening/cyclization deliver p-QBZD 1,2-azide-nitrogen migration. case through regioselective aza-Michael addition/nitrene insertion aldehyde subsequent cyclization imidazole as secondary product without This provides straightforward access redox-active quinone embedded diverse substrate scopes would find potential applications medicinal chemistry discovery.

Language: Английский

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3-Chloropropylbis(catecholato)silicate as a Bifunctional Reagent for the One-Pot Synthesis of Tetrahydroquinolines from o-Bromosulfonamides

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(6), P. 4191 - 4198

Published: Feb. 27, 2024

Bis(catecholato)silicate salts are easily accessible reagents that can be used to install alkyl fragments through photoredox-enabled cross-coupling. These incorporate various functional groups including pendant halides. A halogenated organosilicate reagent was leveraged develop a one-pot synthesis of tetrahydroquinolines from o-bromosulfonamides, where the bifunctional participates in nickel/photoredox cross-coupling followed by intramolecular nucleophilic substitution. The group tolerance this strategy allowed for preparation series substituted tetrahydroquinolines.

Language: Английский

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Pd(II)-Catalyzed 1,2-Oxyarylation of Alkenes with O-Acylhydroxylamines as the Oxygen Source

Organic Letters, Journal Year: 2024, Volume and Issue: 26(18), P. 3691 - 3696

Published: April 25, 2024

O-Acylhydroxylamine has been widely employed as an electrophilic amination reagent in transition-metal-catalyzed C–N coupling reactions, but its use oxygen source not disclosed. Here, we report a Pd-catalyzed 1,2-oxyarylation of alkenes with O-acylhydroxylamines oxidant and for the first time. With simple amide monodentate directing group, this method features broad substrate scope, good functional group tolerance, mild conditions.

Language: Английский

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Pd-Catalyzed Migratory 1,1-Cycloannulation Reaction of Alkenes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 18, 2024

Here, we report a novel strategy for the preparation of diverse heterocycles via Pd-catalyzed migratory 1,1-cycloannulation reaction (MCAR) alkenes. Starting from readily available alkenyl amines and alcohols, this approach allows formation wide range five- to seven-membered azaheterocycles oxaheterocycles with high efficiency good functional group tolerance. The key realization is use 4-iodophenol or 2-iodophenol derivatives where phenolic hydroxyl plays critical role in controlling direction migration ring-size through quinone methide intermediate.

Language: Английский

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Merging Alkene Isomerization Enables Difunctionalization of Cyclic Enamines toward Ring-Fused Aminal Synthesis

Organic Letters, Journal Year: 2023, Volume and Issue: 25(6), P. 992 - 997

Published: Feb. 6, 2023

Here we report a Pd-catalyzed isomerization of alicyclic allyl amine to achieve the unprecedented α,β-difunctionalization synthetically inaccessible trisubstituted cyclic enamine. The dual role in situ formed enamine intermediate allows for intermolecular formal [4 + 2] reaction with acrylamide or isatoic anhydride simultaneously construct C-C bond and C-N bond, thus realizing expedient construction [4.3.0]-aminal excellent diastereoselectivity high atom economy.

Language: Английский

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