A Phosphine-Free Air-Stable Mn(II)-Catalyst for Sustainable Synthesis of Quinazolin-4(3H)-ones, Quinolines, and Quinoxalines in Water

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(8), С. 5250 - 5265

Опубликована: Март 30, 2024

The synthesis, characterization, and catalytic application of a new phosphine-free, well-defined, water-soluble, air-stable Mn(II)-catalyst [Mn(L)(H2O)2Cl](Cl) ([1]Cl) featuring 1,10-phenanthroline based tridentate pincer ligand, 2-(1H-pyrazol-1-yl)-1,10-phenanthroline (L), in dehydrogenative functionalization alcohols to various N-heterocycles such as quinazolin-4(3H)-ones, quinolines, quinoxalines are reported here. A wide array multisubstituted quinazolin-4(3H)-ones were prepared water under air following two pathways via the coupling with 2-aminobenzamides 2-aminobenzonitriles, respectively. 2-Aminobenzyl alcohol ketones bearing active methylene group used partners for synthesizing quinoline derivatives, quinoxaline derivatives by vicinal diols 1,2-diamines. In all cases, reaction proceeded smoothly using our [1]Cl air, affording desired satisfactory yields starting from cheap readily accessible precursors. Gram-scale synthesis compounds indicates industrial relevance synthetic strategy. Control experiments performed understand unveil plausible mechanism.

Язык: Английский

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Phosphine‐Free NNN‐Manganese(II) Catalyzed C‐alkylation of Methyl N‐Heteroarenes via Borrowing Hydrogen

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(7), С. 1531 - 1537

Опубликована: Янв. 31, 2024

Abstract Mn(II)‐catalyzed alkylations of methyl N ‐heteroarenes was reported via borrowing hydrogen strategy with alcohols as the alkylating reagent. The developed geometry‐constrained benzimidazole‐iminopyridyl ligand played a key role in promoting transformation and stablizing metal center. A wide range (aromatic, heteroaromatic aliphatic) ‐Heteroarenes could be able to apply current catalytic system, TON up 7400.

Язык: Английский

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Manganese-catalyzed C–C and C–N bond formation with alcohols via borrowing hydrogen or hydrogen auto-transfer

Beilstein Journal of Organic Chemistry, Год журнала: 2024, Номер 20, С. 1111 - 1166

Опубликована: Май 21, 2024

Transition-metal-mediated "borrowing hydrogen" also known as hydrogen auto-transfer reactions allow the sustainable construction of C-C and C-N bonds using alcohols donors. In recent years, manganese complexes have been explored efficient catalysts in these reactions. This review highlights significant progress made manganese-catalyzed bond-formation via auto-transfer, emphasizing importance this methodology synthesis strategies.

Язык: Английский

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Co‐Catalyzed Dehydrogenation Claisen Condensation of Secondary Alcohols with Esters^†

Chinese Journal of Chemistry, Год журнала: 2024, Номер 42(22), С. 2818 - 2824

Опубликована: Июль 17, 2024

Comprehensive Summary Catalytic dehydrogenation, with its exceptional atom economy and chemoselectivity, offers a highly desirable yet challenging approach for converting multiple environmentally friendly alcohols into crucial molecules. Furthermore, the utilization of catalysts based on abundant elements found Earth alcohol dehydrogenation to produce acryl ketone holds significant promise as versatile strategy in synthesizing key building blocks numerous pharmaceutical applications. The present study describes practical Co‐catalyzed cascade dehydrogenative Claisen condensation secondary esters, facilitating synthesis wide range 3‐hydroxy‐prop‐2‐en‐1‐ones. We introduce catalytic system novel scalable indazole NNP‐ligands coordinated cobalt efficient dehydrogenations alcohols, propose plausible reaction mechanism supported by control experiments labeling studies. Notably, it allows streamlined pharmaceuticals one‐pot.

Язык: Английский

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Oxysulfonylation of Alkynes with Sodium Sulfinates to Access β-Keto Sulfones Catalyzed by BF3·OEt2

Molecules, Год журнала: 2024, Номер 29(15), С. 3559 - 3559

Опубликована: Июль 28, 2024

An efficient and operationally simple method for the synthesis of β-keto sulfones through BF

Язык: Английский

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Manganese‐Catalyzed α‐Alkylation of Sulfones using Alcohols via a Hydrogen‐Borrowing Strategy: Synthesis of Branched Sulfones

Asian Journal of Organic Chemistry, Год журнала: 2024, Номер 13(8)

Опубликована: Май 10, 2024

Abstract Herein, we report an efficient and sustainable manganese‐catalyzed α‐C−H bond alkylation methodology to synthesize branched sulfones via a hydrogen borrowing pathway. The air‐stable phosphine‐free Mn‐catalyst, (NNN)Mn(II)Cl 2 was synthesized by using earth‐abundant, commercially available, inexpensive precursor MnCl .4H O, stable NNN pincer i. e. [N‐((benzimidazole‐2‐yl)methyl)quinoline‐8‐amine] ligand system. Taking benzyl phenyl as substrates, alcohol derivatives alkylating agents, range of were in 40–82 % isolated yields complex the catalyst under open‐air conditions. Control experiments deuterium incorporation studies have also been conducted investigate possible reaction mechanism provide evidence for

Язык: Английский

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Potent pincer-zinc catalyzed homogeneous α-alkylation and Friedländer quinoline synthesis reaction of secondary alcohols/ketones with primary alcohols

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(31), С. 6393 - 6408

Опубликована: Янв. 1, 2024

Herein, we describe an air- and moisture-stable, homogeneous zinc catalyst stabilised using electron deficient N^N^N pincer-type ligand.

Язык: Английский

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A Single Terminal [Ni^II−OH] Catalyst for Direct Julia‐Type Olefination and α‐Alkylation Involving Sulfones and Alcohols

Chemistry - A European Journal, Год журнала: 2024, Номер 30(35)

Опубликована: Апрель 22, 2024

Abstract A terminal [Ni II −OH] complex 1 , supported by triflamide‐functionalized NHC ligands, showed divergent reactivity for the reaction of sulfone with alcohol, contingent on base concentration, temperature, and time. Julia‐type olefination alcohols sulfones was achieved using one equiv. base, whereas lowering loading to 0.5 afforded α ‐alkylated sulfones. Besides excellent substrate scope selectivity, biologically active stilbene derivatives DMU‐212, pinosylvin, resveratrol, piceatannol were synthesized in high yield under conditions. An extensive array controlled experiments DFT calculations provide valuable insight pathway.

Язык: Английский

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Remote C-H Bond Cooperation Strategy Enabled Silver Catalyzed Borrowing Hydrogen Reactions

Chemical Science, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Metal–ligand cooperation (MLC) is an essential strategy in transition metal catalysis. Herein, we demonstrate a remote C–H bond that enables the unprecedented homogeneous Ag( i )-catalyzed BH/HA reaction.

Язык: Английский

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Ruthenium catalyzed dehydrogenative α-C–H functionalization of β-naphthol using alcohols: a metal–ligand cooperative borrowing hydrogen approach

Catalysis Science & Technology, Год журнала: 2024, Номер 14(12), С. 3540 - 3549

Опубликована: Янв. 1, 2024

Chemoselective α-C–H functionalization of β-naphthol is achieved with inexpensive and readily available alcohols using a well-defined, air-stable, easy-to-prepare Ru( ii )-catalyst (1a) bearing redox-active tridentate pincer ( L 1a).

Язык: Английский

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