Stereoselective Construction of Unsymmetrically Linked Heterocycles via Palladium-Catalyzed Alkyne Insertion/Cycloimidoylation Cascade

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(3), P. 1613 - 1624

Published: Jan. 16, 2023

A novel strategy to access unsymmetrically linked heterocycles via palladium-catalyzed acylcycloimidoylation of alkyne-tethered carbamoyl chlorides with isocyanides has been developed. Functionalized were successfully applied as imine-containing heterocycle precursors capture the vinyl-PdII intermediate, which was generated from a syn-carbopalladation alkyne, followed by subsequent intramolecular C-H bond activation/imidoylative Heck reactions. Methylene oxindoles within Z-tetrasubstituted olefins obtained in high yields excellent stereoselectivities. Broad functional groups well tolerated under mild reaction conditions.

Language: Английский

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Immobilizing Stereogenic Nitrogen Center in Doubly Fused Triarylamines through Palladium-Catalyzed Asymmetric C–H Activation/Seven-Membered-Ring Formation

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(14), P. 9688 - 9694

Published: July 10, 2023

A series of doubly fused triarylamines containing conformationally stable stereogenic nitrogen centers has been constructed through palladium-catalyzed enantioselective C–H activation and imidoylative cyclization. The cyclization strategy forming an uncommon seven-membered heterocyclic ring employs readily available functionalized isocyanides aryl iodides as coupling partners under mild conditions. These helically twisted N-chiral frameworks contain no inner helical substituents or other chiral factors that stabilize the pyramidal conformation at nitrogen.

Language: Английский

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Helicoselective Synthesis of Indolohelicenoids through Organocatalytic Central‐to‐Helical Chirality Conversion

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(9)

Published: Jan. 10, 2024

Abstract We report the helicoselective and convergent construction of indolohelicenoids with excellent efficiency stereocontrol. This reaction proceeds through a chiral‐phosphoric‐acid‐catalyzed enantioselective cycloaddition eliminative aromatization sequence, which can be finely controlled by adjusting temperature. Mechanistic studies reveal that chiral phosphoric acid cooperatively serves as both bifunctional Brønsted catalyst, enabling one‐pot central‐to‐helical chirality conversion. Additionally, optical properties synthesized were characterized to explore their potential applications in organic photoelectric materials.

Language: Английский

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Oxidative cyclization of allyl compounds and isocyanide: A facile entry to polysubstituted 2-cyanopyrroles

Chinese Chemical Letters, Journal Year: 2023, Volume and Issue: 35(4), P. 108836 - 108836

Published: July 26, 2023

Language: Английский

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Electrophile-Controlled Regiodivergent Palladium-Catalyzed Imidoylative Spirocyclization of Cyclic Alkenes

Organic Letters, Journal Year: 2024, Volume and Issue: 26(9), P. 1908 - 1913

Published: Feb. 26, 2024

An intermolecular controllable Pd-catalyzed spirocyclization of isocyano cycloalkenes has been developed, offering efficient and selective approaches toward spirocyclic hydropyrrole scaffolds. 2-Azaspiro-1,7-dienes could be obtained through a "chain-walking" process with aryl/vinyl iodides as electrophiles, while the normal Heck product 2-azaspiro-1,6-dienes were selectively generated when aryl triflates used coupling partner isocyanides. Mechanistic studies suggested that counteranion Pd(II) intermediate played crucial role in regioselectivity control. Dihydropyrrole-fused 5,6,7-membered spirocycles switchably accessed under mild conditions wide functional group tolerance.

Language: Английский

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Visible-light promoted radical cascade cyclization of 3-allyl-2-arylquinazolinones for the synthesis of phosphorylated dihydroisoquinolino[1,2-b]quinazolinones

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(62), P. 8119 - 8122

Published: Jan. 1, 2024

A novel visible-light promoted metal-free radical cascade cyclization reaction has been developed with 3-allyl-2-arylquinazolinones as a new class of acceptor. This photocatalytic protocol represents an efficient approach to construct phosphorylated dihydroisoquinolino[1,2-

Language: Английский

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Asymmetric Synthesis of Helicenes from Centrally Chiral Precursors

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(41)

Published: July 19, 2024

Abstract Chiral helicenes are widely used in fields related to organic materials and molecular machines relevant molecules, as well serving privileged frameworks for chiral ligands catalysts. Therefore, the research into asymmetric routes synthesis of helical compounds has garnered significant interest recent years. In this regard, chirality conversion/transfer from precursors emerged a powerful strategy construction helicenes, allowing various types compounds. This become will remain prominent topic field synthesis. review article, described between 2012 2024, approaches by conversion or transfer centrally summarized.

Language: Английский

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Pd-Catalyzed Dual C–H Activation/Cyclization: Convergent and Divergent Synthesis of 1-Azahelicenes

Organic Letters, Journal Year: 2024, Volume and Issue: 26(42), P. 9005 - 9010

Published: Oct. 16, 2024

Herein, we report a convergent synthesis of 1-azahelicenes using easily available quinoline derivatives and cyclic diaryliodonium salts as starting materials. This reaction undergoes palladium-catalyzed dual C-H activation/cyclization process to give facile access wide range 1-aza[5]helicenes 1-aza[6]helicenes with abundant functional groups (including F, Cl, Br, I, CF

Language: Английский

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Catalytic kinetic resolution of helical polycyclic phenols via an organocatalyzed enantioselective dearomative amination reaction

Science Advances, Journal Year: 2024, Volume and Issue: 10(47)

Published: Nov. 22, 2024

Despite the considerable potential applications for helically chiral molecules across various sectors, their catalytic asymmetric synthesis remains nascent and has seen very limited advancement compared to that of central axial compounds, primarily owing scarcity available starting materials immense challenges associated with achieving stereochemical control. Herein, we report an innovative approach facile kinetic resolution uniquely structured stereochemically complex helical polycyclic phenols by using a steric hindrance–regulated enantioselective dearomative amination reaction. The distinguished aspects this method include exceptional stability dearomatized products impressive versatility recovered substrates in construction enantioenriched frameworks. This work showcases strategic incorporation appropriate groups near reaction site electron-rich aromatic compound can indeed enable interrupted Friedel-Crafts reaction, thus opening alternate avenue study dearomatization nonfunctionalized arenes.

Language: Английский

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DFT-Assisted Atroposelective Construction of Indole-Fused N-Heteroaromatic Frameworks through Palladium-Catalyzed C–H Imidoylation

ACS Catalysis, Journal Year: 2024, Volume and Issue: 15(1), P. 201 - 210

Published: Dec. 16, 2024

On the basis of density functional theory (DFT) calculations, we designed an asymmetric synthesis method for axially chiral biaryls through C(sp2)–H imidoylative cyclization isocyanides. Building on this, successfully synthesized compounds containing indole-fused N-heteroaromatic frameworks via palladium-catalyzed C–H imidoylation to achieve high yields and enantioselectivity. Various efficient pathways facilitated ring derivatives with either C–C or C–N axial chirality. This not only provides diverse strategy but also demonstrates that DFT-assisted design is a reliable tool accurately predicting reaction stereoselectivity effectively reducing workload chemical experiments.

Language: Английский

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