Transition-Metal-Catalyzed Carbonylative Multifunctionalization of Alkynes

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 88(8), P. 4975 - 4994

Published: June 16, 2022

Currently, the construction of new carbon–carbon bonds and value-added structures in an atom- step economical manner has become a continuous pursuit synthetic chemistry community. Since first transition-metal-catalyzed hydroformylation ethylene was reported by Otto Roelen 1930s, impressive progress been achieved carbonylative functionalization unsaturated C–C bonds. In contrast to alkenes, alkynes offers tremendous potential for multisubstituted carbonyl-containing derivatives because their two independently addressable π-systems. This review provides timely necessary investigation mutifunctionalization with exclusion hydrofunctionalizations. Different transition metals including palladium, rhodium, iridium, ruthenium, iron, copper, etc. were applied development novel transformation. Various C–C, C–N, C–O, C–S, C–B, C–Si, carbon–halogen formed efficiently give corresponding tri- or tetrasubstituted α,β-unsaturated ketones, diesters, heterocycles.

Language: Английский

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Electrocatalytic three-component synthesis of 4-halopyrazoles with sodium halide as the halogen source

Organic & Biomolecular Chemistry, Journal Year: 2022, Volume and Issue: 20(43), P. 8501 - 8505

Published: Jan. 1, 2022

The first example of the electrocatalytic multicomponent synthesis 4-chloro/bromo/iodopyrazoles from hydrazines, acetylacetones and sodium halides under chemical oxidant- external electrolyte-free conditions has been developed.

Language: Английский

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Merging Iron-Mediated Radical Ligand Transfer (RLT) Catalysis and Mechanochemistry for Facile Dihalogenation of Alkenes

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 13747 - 13758

Published: Aug. 30, 2024

With the growing emphasis on cost- and atom-economical chemical synthesis, mechanochemistry has attracted considerable attention for providing environmentally friendly alternatives to traditional solvent-based organic transformations. Herein, we demonstrate use of facilitate alkene dihalogenation via iron-mediated radical ligand transfer (RLT) catalysis, producing diverse vicinal dichloro, dibromo, bromochloro molecules. The method is characterized by its simplicity, rapid reaction time, high chemo- regioselectivity, broad functional group tolerance, accommodating both activated unactivated alkenes alkynes. Mechanistic insights suggest nature these processes, underscoring effectiveness mechanochemically driven RLT catalysis modular functionalization unsaturated hydrocarbons.

Language: Английский

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Palladium-Catalyzed Denitrogenative Carbonylation of Benzotriazoles with Cr(CO)₆ as the Carbonyl Source

Organometallics, Journal Year: 2022, Volume and Issue: 41(13), P. 1731 - 1737

Published: June 23, 2022

A general palladium and silver co-catalyzed denitrogenative carbonylation of benzotriazoles for the synthesis benzoxazin-4-ones has been developed. Employing as easily accessible substrates Cr(CO)6 bench-stable solid carbonyl sources, various were synthesized through a ring-opening/denitrogenative/carbonylation cascade processes in moderate to good yields. Notably, this protocol avoids use toxic CO gas special equipment can also be applied late-stage functionalization derived from uricosuric agent probenecid.

Language: Английский

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Palladium‐Catalyzed Reductive Double Carbonylation of Nitroarenes with Aryl Halides Using Mo(CO)₆ as a Reductant and Carbonyl Source

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 29(2)

Published: Sept. 30, 2022

A new palladium-catalyzed reductive double carbonylation of nitroarenes with aryl halides for the synthesis benzoxazin-4-ones has been reported. The key to success was use Mo(CO)6 as a reductant and bench-stable solid carbonyl sources. Various iodides, bromides, trifluoromethanesulfonates are suitable reaction partners produce corresponding benzoxazin-4-one derivatives in moderate good yields. Preliminary mechanistic studies indicate that nitrosoarene first generated intermediate through nitro reduction. Remarkably, this method avoids toxic CO gas is further applied late-stage modification estrone.

Language: Английский

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Electrochemical Trifluoromethylation and Sulfonylation of N-Allylamides: Synthesis of Oxazoline Derivatives

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(17), P. 12630 - 12640

Published: Aug. 14, 2023

We report a new method for the synthesis of trifluoromethylated and sulfonylated oxazolines by electrochemical radical cascade cyclizations N-allylamides with sodium trifluoromethanesulfinate or sulfonylhydrazines. This protocol provides green useful strategy to synthesize broad substrate scope under ambient conditions.

Language: Английский

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Electrode-switchable: exploring this new strategy to achieve regiodivergent azidoiodination of alkenes

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(8), P. 2189 - 2194

Published: Jan. 1, 2024

An “electrode-switchable” organic electrochemistry method for the azidoiodination of alkenes, where choice anode dictates regiodivergent alkene azidoiodination, reveals a novel pathway controlled regioisomers.

Language: Английский

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Radical Esterification of Unactivated Alkenes Using Formate as Carbonyl Source

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(7), P. 4918 - 4925

Published: March 22, 2022

In recent years, methyl formate has received considerable attention as an ideal and green C1 building block to synthesize carboxylic esters. However, examples of a one-step route esters with one-carbon elongation using source methoxycarbonyl radical are still rare. Herein, we present peroxide-induced carbonylation N-(2-methylallyl)benzamides the precursor RuCl3 catalyst, affording series biologically valuable 4-[(methoxycarbonyl)methyl]-3,4-dihydroisoquinolinones good tolerance insensitivity moisture in one pot under simple mild conditions.

Language: Английский

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Sustainability in a can: upcycling aluminium scrap in the waste-minimized electrochemical synthesis of 2-oxazoline

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(13), P. 8030 - 8036

Published: Jan. 1, 2024

We present herein the utilization of electrodes made from secondary aluminium sources and achieving waste minimized, oxidant-free, electro-synthesis 2-oxazolines.

Language: Английский

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Synthesis of 3-chloropiperidines by iodide-mediated electrolysis

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(18), P. 4631 - 4636

Published: Jan. 1, 2023

We report a method for the electroorganic synthesis of 3-chloropiperidines in an undivided cell at room temperature. Through use TBAI as redox mediator, reaction proceeds without oxidant stoichiometric quantity.

Language: Английский

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