Facile Construction of Quaternary Carbon Centers via Dinuclear Titanium(III)‐Catalyzed Reductive Coupling of Tertiary Chlorides and Activated Olefins

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(20)

Published: June 19, 2024

Abstract The establishment of all‐carbon quaternary carbon centers represents a pivotal aspect in the synthesis numerous natural products and pharmaceutical compounds, underscoring its paramount significance synthetic organic chemistry. Herein, we present novel strategy for generation through reductive coupling tertiary halides, catalyzed by dinuclear (salen)titanium catalysts. This catalytic framework demonstrates notable reactivity towards chlorides while maintaining inertness secondary primary chlorides, thereby facilitating exceptional chemoselectivity C−C bond formation. reaction proceeds with remarkable efficiency across diverse range substrates under mild conditions.

Language: Английский

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Mechanically Enabled Formal Reductive Cross-Coupling Reaction of Two Inert Bonds

Research Square (Research Square), Journal Year: 2024, Volume and Issue: unknown

Published: June 19, 2024

Reductive cross-coupling reactions involving two electrophilic reagents have become increasingly important in modern synthetic chemistry. Previous studies investigated featuring zero or one inert bond; however, with bonds remain unexplored. This study presents the inaugural nickel-catalyzed reductive reaction induced by mechanical force, aryl ethers and fluorides, both of which contain bonds. results successful assembly a series versatile biaryl compounds demonstrates excellent tolerance for various functional groups. novel coupling offers innovative approaches polymer degradation development luminescent materials.

Language: Английский

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Iridium-Pentahydride Referee for Competition of Activations between C–H and C–F Bonds and between C–H Bonds Located in Different Positions

Organometallics, Journal Year: 2024, Volume and Issue: 43(17), P. 1869 - 1878

Published: Aug. 9, 2024

Polyhydride IrH5(PiPr3)2 (1) activates an ortho-CH bond of acetophenone and ortho-CF 2,3,4,5,6-pentafluoroacetophenone to give IrH2{κ2-C,O-[C6H4C(O)CH3]}(PiPr3)2 (2) IrH2{κ2-C,O-[C6F4C(O)CH3]}(PiPr3)2 (3). When the phenyl group contains bonds, activation is kinetically favored. Thus, complexes IrH2{κ2-C,O-[C6H3FC(O)CH3]}(PiPr3)2 (4) IrH2{κ2-C,O-[C6H4C(O)C6H3F2]}(PiPr3)2 (5) are obtained from reactions 1 with 2-fluoroacetophenone 2,6-difluorobenzophenone. Complex also 4-fluorophenyl 2-(4-fluorophenyl)pyridine. The reaction leads IrH2{κ2-C,N-[C6H3F-py]}(PiPr3)2 (6). Replacement hydrogen atom one bonds a fluorine accelerates orthometalation, while compete for metal center. 2-(2,4-difluorophenyl)pyridine produces 1:9 mixture 6 IrH2{κ2-C,N-[C6H2F2-py]}(PiPr3)2 (7). in competitive manner 2,6-bis(2,4-difluorophenyl)pyridine mixtures IrH{κ3-C,N,C-[C6H2F2-py-C6H2F2]}(PiPr3)2 (8) IrH{κ3-C,N,C′-[C6H2F2-py-C6H3F]}(PiPr3)2 (9). H/D Isotopic exchange experiments indicate that these orthometalations thermodynamically assisted by chelating effect resulting coordination carbonyl or pyridyl groups. However, other C(sp2)–H less sterically hindered distribution deuterium atoms orthometalated ring shows kinetic preference located ortho fluorine.

Language: Английский

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One‐pot Synthesis of Thioamides via Nickel‐Catalyzed Coupling of Thiocarbamoyl Fluorides and Boronic Acids

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

Published: Aug. 16, 2024

Abstract A novel and efficient one‐pot method has been developed for the synthesis of thioamides through coupling reactions between thiocarbamoyl fluorides, which are generated in situ from amines, boronic acids. The key to success this transformation lies use nickel a catalyst combined with PCy 3 as ligand. This innovative reaction protocol provides mild conditions suitable producing diverse array thioamides, late‐stage modification amoxapine was successfully achieved.

Language: Английский

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Catalytic Synthesis of Fluoroalkyl Ketones

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(23)

Published: Aug. 27, 2024

Abstract Fluoroalkyl ketones are a class of structural motifs which ubiquitous in bioactive molecules, and serve as synthons for diverse value‐added fluorine‐containing targets. The presence fluorine significantly alters the lipophilicity bioactivity alkyl well imposes additional challenges on synthesis fluoroalkyl ketones. Traditional methods heavily rely multiple‐step manipulations require stoichiometric reagents suffer from low efficiency. Thus, development synthesizing enabled by catalytic is highly valuable yet challenging. This Concept summarizes recent renaissance developing with substitution patterns different precursors. In addition, further efforts method also discussed.

Language: Английский

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