Merging Photoinduced Electron Transfer with Hydrogen Atom Transfer: Formal β-C(sp³)–H Pyridination of Carbonyls

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

Published: Jan. 9, 2025

In this study, a novel approach that combines photoinduced electron transfer (ET) with hydrogen atom (HAT) has been introduced for the selective β-C(sp3)–H pyridination of carbonyl compounds. This method is notable its absence transition metals and ability to function under benign reaction conditions, resulting in range pyridinated derivatives consistently moderate good yields. The significance technique further underscored by potential late-stage functionalization pharmaceutically significant molecules. Mechanistic investigations confirmed proceeds via radical-mediated pathway.

Language: Английский

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Methyl Ketones as Alkyl Halide Surrogates: A Deacylative Halogenation Approach for Strategic Functional Group Conversions

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(38), P. 21096 - 21103

Published: Sept. 15, 2023

Alkyl halides are versatile precursors to access diverse functional groups (FGs). Due their lability, the development of surrogates for alkyl is strategically important complex molecule synthesis. Given stability and ease derivatization inherent in common ketones, here we report a deacylative halogenation approach convert various methyl ketones corresponding chlorides, bromides, iodides. The reaction driven by forming an aromatic byproduct, i.e., 1,2,4-triazole, which N′-methylpicolinohydrazonamide (MPHA) employed form prearomatic intermediate halogen atom-transfer (XAT) reagents used quench radical intermediate. efficient yielding primary secondary from wide range with broad FG tolerance. It also works natural-product-derived fluoro-containing substrates. In addition, one-pot conversions other FGs annulations alkenes alkynes through realized. Moreover, unusual iterative homologation iodides demonstrated. Finally, mechanistic studies reveal intriguing double XAT process iodination reaction, could have implications beyond this work.

Language: Английский

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Magnetic MoS₂ efficient heterogeneous photocatalyst for the α-methoxymethylation and aminomethylation of aromatic ketones

Catalysis Science & Technology, Journal Year: 2022, Volume and Issue: 13(3), P. 665 - 674

Published: Dec. 5, 2022

Magnetic MoS 2 quantum dots are designed and applied as an efficient photocatalyst for the α-methoxymethylation aminomethylation of aromatic ketones using methanol a green C1 source in air under visible-light irradiation at room temperature.

Language: Английский

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Copper catalyzed C(sp3)–H/C(sp3)–H cross-coupling of arylacetic acid equivalents with methylarenes via α-carbonyl radicals

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Arylacetic acid equivalents, bearing a pyridine group, undergo copper-catalyzed C(sp 3 )–H/C(sp )–H cross-coupling with methylarenes to give α,β-diarylpropionic acids via the formation of α-carbonyl radicals.

Language: Английский

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Mechanisms of C(sp³)-H Functionalization of Acetonitrile or Acetone with Alkynes: A DFT Investigation

Journal of Chemical Information and Modeling, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 6, 2025

The mechanisms for the C(sp3)-H activation and addition reactions between acetonitrile (or acetone) alkynes have been investigated with M06-2X-D3/ma-def2-TZVP method basis set. SMD (solvation model based on solute electron density) was applied to simulate solvent effect. In first second reactions, 2-phenylbut-3-yn-2-ol reacted acetone, respectively. First, activations of acetone could be achieved by PhCOO• t-BuO• radicals. Then, converted into final products P1 P2. Gibbs free energy surfaces these two suggest that blue lines would favorable paths lower barriers, terminal C atom C≡C bond is best reactive site. Moreover, analysis IRI (Interaction Region Indicator) reveals Z- E-configuration transformations. While in third fourth methyl(2-(phenylethynyl)phenyl)sulfane has interactions via some paths, profiles show C10 atom, rather than C11 priority, are favorable. Furthermore, action mode Na2HPO4 reduce barrier benefit reaction. vdW (van der Waals) play an important role choice fifth sixth) reaction, it happened 1-(2-(methylthio)phenyl)-3-phenylprop-2-yn-1-one acetontrile yield product P5 P6). computational results uncovered line path, site depends interactions, which origin selectivity. addition, investigation byproducts carried out, can explain reason only main produced. Both those agree experimental results. localized orbital locator (LOL) isosurfaces, Laplacian order (LBO), density critical point (ρBCP), spin isosurface graphs, graphs used analyze structure reveal reaction substances.

Language: Английский

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Mild Hydroalkylation of Terminal Olefins Via Decatungstate/Thiol Cooperative Photocatalysis

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

Published: April 23, 2025

Here we report the use of a tetrabutylammonium decatungstate (TBADT)/thiol photocatalytic system for selective addition acetone and other simple ketone, nitrile, chlorocarbon functionalities to terminal olefins. This avoids energetic reagents such as peroxides proceeds under mild conditions using Earth-abundant element catalysts, providing sustainable approach C-C bond formation activated Initial exploration reveals that hydroalkylation unactivated olefins is also possible, though in lower efficiency, preliminary mechanistic experiments are consistent with radical mechanism.

Language: Английский

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Visible-light-mediated oxidant-free tandem acylmethylation/ipso-spirocyclization of N-arylpropiolamides: Access to 3-acylmethyl azaspiro[4,5]trienones

Molecular Catalysis, Journal Year: 2025, Volume and Issue: 582, P. 115120 - 115120

Published: May 2, 2025

Language: Английский

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Breast cancer cell targeting of L-leucine-PLGA conjugated hybrid solid lipid nanoparticles of betulin via L-amino acid transport system-1

Journal of drug targeting, Journal Year: 2025, Volume and Issue: unknown, P. 1 - 32

Published: May 3, 2025

The aim of fabricating hybrid solid lipid nanoparticles (HSLN) was to enhance the delivery betulin triple negative beast cancer cells through intravenous route via L-amino transporter system-1, using L-leucine-PLGA conjugate (Conj-HSLN) by hot high pressure homogenization method. Betulin (BN), having potent anticancer and antioxidant activity, faces challenges due poor water solubility permeability, affecting its bioavailability. results revealed Conj-HSLN with particle size 318.3 ± 0.25 nm. percent cumulative BN release from 57.763%, 24h. cytotoxicity study in MB-MDA-231 cell depicts, LD50 67.73 µg/ml Conj-HSLN. Pharmacokinetics reveals enhanced Cmax half-life (32.12 µg/ml, 4.72 0.53 h) than raw (1.31 0.21 7.54 0.34 h). Enhanced distribution at tumor site (11.5967% ID, 2h) signifies role L-leucine transport system. Pharmacodynamic shows mean volume 765.3 85.884, 1450.01 219.361 mm3 Conj-HSLN, respectively 3rd week treatment. Standardized uptake value attributed reduced glucose uptake, inhibited growth proliferation, confirmed biomarkers assay, VEGF Caspase-9. In conclusion, targeted controlled conjugated-BN loaded HSLN is stable, safe, effective against breast cancers.

Language: Английский

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C-centered radical-initiated cyclization by directed C(sp³)–H oxidative functionalization

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(20), P. 5726 - 5757

Published: Jan. 1, 2022

C(sp 3 )–H functionalization is attracting constant attention. This review emphasizes C-centered radicals initiated cyclization strategies by directed oxidative since 2012.

Language: Английский

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Straightforward α-allylation of carbonyl compounds with alkenes via α-carbonyl radical intermediates

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(9), P. 2502 - 2511

Published: Jan. 1, 2024

We report that the direct oxidative cross-coupling of carbonyl compounds with simple alkenes is realized to synthesize α-allylated by identifying bisphosphine ligand BINAP enables copper catalyst integrate two different catalytic cycles in a one-pot system.

Language: Английский

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