Cp*Co(III)-catalyzed ortho-alkylation/alkenylation of anilides

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A highly practical and efficient Cp*Co( iii )-catalyzed regioselective C–H alkylation/alkenylation of anilides with maleimides acrylates was developed, during which a weakly coordinating amide group functioned as the directing group.

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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Co(III)-Catalyzed Regioselective Functionalization of Isoquinolones with Naphthoquinones

Organic Letters, Journal Year: 2024, Volume and Issue: 26(23), P. 5027 - 5031

Published: June 3, 2024

A strategy for Co(III)-catalyzed C(sp

Language: Английский

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Rh(III)-Catalyzed Regioselective C(sp2)-H alkenylation of isoquin-olones with methoxyallene: A Facile Access to aldehyde bearing iso-quinolones

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(32), P. 6612 - 6616

Published: Jan. 1, 2024

A simple and rapid access to isoquinolone aldehyde scaffolds has been established by a rhodium-catalyzed reaction between methoxyallene that forges alkenylation in an explicit regioselective manner. Herein, serving as acrolein equivalent results execution of this unique functionalization. Furthermore, the compatibility with complex molecules underscores significance developed protocol. The mechanistic proposal for transformation was consistent kinetic studies several control reactions.

Language: Английский

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Ru(II)‐Catalyzed C8 Alkenylation of Isoquinolones with Allyl Alcohol

Asian Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 9, 2024

Abstract A simple Ru(II)‐catalyzed protocol for the alkenylation of isoquinolones with readily accessible allyl alcohols to generate aldehyde bearing has been developed. The use green solvent like dimethyl carbonate makes this method environment‐friendly. Experimental studies were carried out support proposed mechanism. reaction was scaled up showcase application current method.

Language: Английский

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