Beyond Tertiary Amines: Introducing Secondary Amines by Palladium/Norbornene‐Catalyzed Ortho Amination

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(24)

Published: April 5, 2024

Since the discovery of palladium/norbornene (Pd/NBE)-catalyzed ortho amination in 2013, escaping limitation only yielding tertiary anilines has been a long-standing challenge. Here, we describe that, by carefully choosing phosphine ligand and NBE mediator, installation N-mono-alkylamino group becomes feasible. The reaction tolerates wide range aryl iodide substrates various N-mono-tertiary alkylamine-derived electrophiles. Both ipso alkenylation alkynylation can be realized. synthetic utility this method is exemplified formation primary amino via selective deprotection streamlined access to N-heterocycles. Preliminary success installing bulky N-secondary alkylamino mechanistic understanding decomposition pathways mono N-alkylamine electrophiles have obtained.

Language: Английский

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Nucleophile-Controlled Trapping of Gold Carbene by Nitriles and Water: Synthesis of 5H-Pyrimido[5,4-b]indoles and 2-Benzylidene-3-indolinones

Organic Letters, Journal Year: 2024, Volume and Issue: 26(3), P. 631 - 635

Published: Jan. 12, 2024

A gold-catalyzed, nucleophile-controlled cascade reaction of N-(2-azidophenyl-ynyl)methanesulfonamides with nitriles and water is described that provides structurally diverse 5H-pyrimido[5,4-b]indoles 2-benzylidene-3-indolinones in good to excellent yields. Mechanistic studies indicate the β-sulfonamido-α-imino gold carbene key intermediate which generated through gold-catalyzed cyclization undergoes formal [4 + 2] annulation intramolecular SN2′ type water, respectively.

Language: Английский

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Cu(im) ₂ -derived Cu@N–C catalyst for one-pot synthesis of 2-substituted indoles via domino Sonogashira coupling-cyclization reactions

Green Chemistry Letters and Reviews, Journal Year: 2024, Volume and Issue: 17(1)

Published: Jan. 10, 2024

Cu(im)2-derived Cu@N–C(600) catalyst has been efficiently utilized for the preparation of N-tosyl(H)−2-substituted indoles through one-pot domino Sonogashira coupling-cyclization reactions between N-tosyl(acetyl)−2-iodo anilines and aryl acetylenes. The catalytic system was heterogeneous showed excellent functional group compatibility could be performed well, affording corresponding coupling products in good to yields.

Language: Английский

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Double-Brønsted acidic deep eutectic solvents and their applications as solvents and catalysts in chemical transformations

Journal of Molecular Liquids, Journal Year: 2025, Volume and Issue: unknown, P. 127110 - 127110

Published: Feb. 1, 2025

Language: Английский

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Enantioselective Synthesis of Spirocyclic Isoxazolones Using a Conia-Ene Type Reaction

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 5, 2025

Stereoselective synthesis of spirocyclic compounds containing heterocyclic motifs represents a formidable challenge in enantioselective synthesis. Here, we present cascade reaction between α,β-unsaturated aldehydes and isoxazolones under synergistic catalysis chiral secondary amine palladium(0) catalyst. This strategy allows access to spiroisoxazolone derivatives with large substrate scope tolerance high levels diastereoselectivity (dr up 20:1) enantioselectivity (up 99% ee). Furthermore, the utility this methodology is showcased by transformation spiroisoxazolones into structurally attractive enantiomerically enriched cyclopentene carboxylic acids two stereogenic centers.

Language: Английский

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Gold‐Catalyzed Alkyne‐Amine Cascade Annulations: A Modern Strategy for Azaheterocycle Construction

The Chemical Record, Journal Year: 2025, Volume and Issue: unknown

Published: April 7, 2025

Abstract Gold catalysis has experienced remarkable progress over the past two decades, particularly in transformations involving alkynes. While numerous aspects of gold‐catalyzed reactions have been extensively reviewed, specific area cascade annulations between functionalized amines and alkynes represents a distinct rapidly developing direction that warrants focused attention. This survey collects systematically analyzes these transformations, which emerged as convenient synthetic strategies to diverse nitrogen heterocycles. The relevant are classified firstly by chemical nature amine functional substituent, secondly size formed ring. field under consideration bridges several fundamental practical branches chemistry, including catalysis, organic synthesis, medicinal materials science.

Language: Английский

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Syntheses of Tetracyclic Indoline Derivatives Via Gold(I)-Catalyzed Hydroamination/Cycloisomerization Cascade of 2-Ethynyltryptamides

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(5), P. 3331 - 3344

Published: Feb. 16, 2024

A gold(I)-catalyzed hydroamination/cycloisomerization cascade reaction was developed to yield indolizino[8,7-b]indole and indolo[2,3-a]-quinolizine derivatives from 2-ethynyltryptamides. The optimal conditions were determined by condition screening, the functional group tolerances of these reactions explored based on synthetic substrates. An insight into explanation selectivity ring closure obtained density theory calculations. plausible mechanism for proposed. Derivatization total synthesis nauclefidine demonstrated practicality this strategy.

Language: Английский

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Gold Salts as Alternative Catalysts in Promoting Cascade Condensation of 2-Aminobenzaldehydes with Alcohols and Amines

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(22), P. 16828 - 16837

Published: Oct. 30, 2024

The distinctive features of gold self-relay catalysts were alternatively utilized in the intriguing cascade condensation 2-aminobenzaldehydes with alcohols and amines. Using NaAuCl4·2H2O as a catalyst, range 13-alkyloxy-7,11b-dihydro-6H,13H-6,12-[1,2]benzenoquinazolino[3,4-a]quinazoline derivatives was produced good to high yields through A3B various alcohols. By carefully choosing reaction conditions, catalysis also proved effective for A2B primary aryl- benzylamines, facilitating synthesis challenging McGeachin bisaminals, including chiral nonracemic derivative 2-(S)-methylbenzylamine. mild conditions this gold-catalyzed approach may lead new advancements field.

Language: Английский

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Gold-Catalyzed “Back-to-Front” Synthesis of 4-Silyloxyindoles

Organic Letters, Journal Year: 2024, Volume and Issue: 26(23), P. 4969 - 4974

Published: June 5, 2024

A series of pyrrol-yn-glycol derivatives were easily prepared from simple pyrroles through a three-step sequence involving hydroxyalkylation-alkynylation-

Language: Английский

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Development of a flow photochemical process for a π-Lewis acidic metal-catalyzed cyclization/radical addition sequence: in situ-generated 2-benzopyrylium as photoredox catalyst and reactive intermediate

Beilstein Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 20, P. 1973 - 1980

Published: Aug. 13, 2024

A flow photochemical reaction system for a π-Lewis acidic metal-catalyzed cyclization/radical addition sequence was developed, which utilizes in situ-generated 2-benzopyrylium intermediates as the photoredox catalyst and electrophilic substrates. The key were generated through intramolecular cyclization of

Language: Английский

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