Sulfonamides as N-Centered Radical Precursors for C–N Coupling Reactions To Generate Amidines

Organic Letters, Journal Year: 2024, Volume and Issue: 26(18), P. 3855 - 3860

Published: April 30, 2024

Nitrogen-centered radicals (NCRs) are valuable intermediates for the construction of C-N bonds. Traditional methods generation NCRs employ toxic radical initiators, transition metal catalysts, photocatalysts, or organometallic reagents. Herein, we report a novel strategy toward bonds under transition-metal-free conditions. Thus, super-electron-donor (SED) 2-azaallyl anions undergo single-electron transfer (SET) with sulfonamides, forming aminyl (R

Language: Английский

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One-Pot Synthesis of Indolin-3-ones Mediated by LiN(SiMe₃)₂/CsF

Organic Letters, Journal Year: 2024, Volume and Issue: 26(24), P. 5082 - 5086

Published: June 7, 2024

Indolin-3-ones are essential heterocycles with wide-ranging biological activities and medicinal values, therefore, efficient approaches to their synthesis remain in demand. Herein, a novel operationally simple method generate indolin-3-ones is reported by using tandem reaction of N-methylbenzylamines methyl 2-fluorobenzoates mediated the LiN(SiMe3)2 CsF system (34 examples, 30–85% yields). The C2-quaternary indolin-3-one further demonstrated potential practicability these reactions.

Language: Английский

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Synthesis of Indolines via Base‐Mediated C–H Activation and Defluorinative C–N Coupling, with no Need for Transition‐Metals

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(37)

Published: May 2, 2024

Abstract Syntheses of (partially) aromatic nitrogen heterocycles increasingly rely on transition‐metal catalyzed C−C‐ and C−N‐cross‐coupling reactions. Here we describe a different approach to the synthesis indolines by domino C(sp 3 )−H activation, 1,2‐addition, defluorinative S N Ar‐cyclization sequence provide target 1,2‐diarylindolines (1,2‐diaryl‐2,3‐dihydroindoles) from ortho ‐fluorinated methyl‐arenes ‐aryl imines (benzylidene anilines) in cyclocondensation that is mediated potassium hexamethyldisilazide (KHMDS) as base exclusively. This transition‐metal‐free process via C−H C−F bond activation provides one‐step entry into wide array indoline scaffolds (43 examples, up 96 % yield). privileged substructure common natural products pharmaceuticals alike, cannot be accessed traditional condensation

Language: Английский

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One-pot transition-metal-free synthesis of alkynes and enynes

Cell Reports Physical Science, Journal Year: 2024, Volume and Issue: 5(8), P. 102132 - 102132

Published: Aug. 1, 2024

Alkynes are key motifs in chemistry, serving as precursors many organic reactions toward the synthesis of bioactive compounds, polymers, and new materials. Methods to synthesize terminal alkynes with an extension carbon skeleton involve harsh and/or dangerous reagents. Further derivatization diaryl largely relies on popular Sonogashira coupling. This cross-coupling uses expensive Pd catalysts, phosphine ligands, toxic Cu co-catalysts. Herein, we report a one-pot approach under transition-metal-free conditions from feedstock chemicals (toluenes methyl benzoates). is also applicable preparation conjugated 1,3-enynes single flask. The disclosed methods expected be complementary state-of-the-art by streamlining alkynes, reducing costs production these valuable building blocks, increasing sustainability alkynes.

Language: Английский

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Sodium Alkyl(trimethylsilyl)amides: Substituent- and Solvent-dependent Solution Structures and Reactivities

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(44), P. 30397 - 30421

Published: Oct. 24, 2024

The preparation of sodium isopropyl(trimethylsilyl)amide (NaPTA), (1-phenylethyl)(trimethylsilyl)amide (NaPETA),

Language: Английский

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Base-Promoted Synthesis of Isoquinolines through a Tandem Reaction of 2-Methyl-arylaldehydes and Nitriles

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(10), P. 6793 - 6797

Published: May 1, 2024

A convenient method for preparing 3-aryl isoquinolines via a base-promoted tandem reaction is presented. Simply combining commercially available 2-methyl-arylaldehydes, benzonitriles, NaN(SiMe

Language: Английский

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