Alcohols as Substrates in Transition-Metal-Catalyzed Arylation, Alkylation, and Related Reactions

Chemical Reviews, Год журнала: 2024, Номер 124(9), С. 6078 - 6144

Опубликована: Апрель 17, 2024

Alcohols are abundant and attractive feedstock molecules for organic synthesis. Many methods their functionalization require them to first be converted into a more activated derivative, while recent years have seen vast increase in the number of complexity-building transformations that directly harness unprotected alcohols. This Review discusses how transition metal catalysis can used toward this goal. These broadly classified three categories. Deoxygenative functionalizations, representing derivatization C–O bond, enable alcohol act as leaving group formation new C–C bonds. Etherifications, characterized by O–H represent classical reactivity has been modernized include mild reaction conditions, diverse partners, high selectivities. Lastly, chain reactions described, wherein acts mediator formal C–H alkyl backbone. Each these classes transformation will discussed context intermolecular arylation, alkylation, related reactions, illustrating alcohols harnessed

Язык: Английский

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Well-Defined Phosphine-Free Manganese(II)-Complex-Catalyzed Synthesis of Quinolines, Pyrroles, and Pyridines

The Journal of Organic Chemistry, Год журнала: 2022, Номер 87(13), С. 8351 - 8367

Опубликована: Июнь 21, 2022

Herein, we report a simple, phosphine-free, and inexpensive catalytic system based on manganese(II) complex for synthesizing different important N-heterocycles such as quinolines, pyrroles, pyridines from amino alcohols ketones. Several control experiments, kinetic studies, DFT calculations were carried out to support the plausible reaction mechanism. We also detected two potential intermediates in cycle using ESI-MS analysis. Based these metal-ligand cooperative mechanism was proposed.

Язык: Английский

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Iridium-Catalyzed Enantioconvergent Borrowing Hydrogen Annulation of Racemic 1,4-Diols with Amines

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(9), С. 5007 - 5016

Опубликована: Фев. 21, 2023

We present an enantioconvergent access to chiral N-heterocycles directly from simple racemic diols and primary amines, through a highly economical borrowing hydrogen annulation. The identification of amine-derived iridacycle catalyst was the key for achieving high efficiency enantioselectivity in one-step construction two C-N bonds. This catalytic method enabled rapid wide range diversely substituted enantioenriched pyrrolidines including precursors valuable drugs such as aticaprant MSC 2530818.

Язык: Английский

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Ruthenium pincer complex catalyzed efficient synthesis of quinoline, 2-styrylquinoline and quinazoline derivatives via acceptorless dehydrogenative coupling reactions

Catalysis Science & Technology, Год журнала: 2022, Номер 12(18), С. 5695 - 5702

Опубликована: Янв. 1, 2022

The synthesis of N-heterocycles has been considered an emerging area chemical research due to their extensive utilization in pharmaceuticals, materials science, and natural product synthesis.

Язык: Английский

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Photochemical dehydrogenation of N-heterocycles over MOF-supported CdS nanoparticles with nickel modification

Applied Catalysis B Environment and Energy, Год журнала: 2022, Номер 317, С. 121708 - 121708

Опубликована: Июль 5, 2022

Язык: Английский

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A general and practical bifunctional cobalt catalytic system for N-heterocycle assembly via acceptorless dehydrogenation

Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(17), С. 4554 - 4560

Опубликована: Янв. 1, 2022

A novel and highly-efficient N-heterocycle assembly methodology catalyzed by a cobalt- N , -bidentate complex via acceptorless dehydrogenation coupling of alcohols amines has been established.

Язык: Английский

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Zn(II)-Catalyzed Multicomponent Sustainable Synthesis of Pyridines in Air

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(6), С. 3650 - 3665

Опубликована: Фев. 28, 2023

Herein, we report a Zn(II)-catalyzed solvent-free sustainable synthesis of tri- and tetra-substituted pyridines using alcohols as the primary feedstock NH4OAc nitrogen source. Using well-defined air-stable Zn(II)-catalyst, 1a, featuring redox-active tridentate azo-aromatic pincer, 2-((4-chlorophenyl)diazenyl)-1,10-phenanthroline (La), wide variety unsymmetrical 2,4,6-substituted were prepared by three-component coupling secondary with NH4OAc. Catalyst 1a is equally compatible four-component coupling. Unsymmetrical also via alcohol two different A series up to 67% yield 1-phenylpropan-1-one or 1,2-diphenylethan-1-one The 1a-catalyzed reactions proceeded efficiently upon replacing corresponding ketones, producing desired in higher yields shorter reaction time. few control experiments performed unveil mechanistic aspects, which indicates that active participation aryl-azo ligand during catalysis enables Zn(II)-complex act an efficient catalyst for present multicomponent reactions. Aerial oxygen acts oxidant dehydrogenation alcohols, H2O H2O2 byproducts.

Язык: Английский

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Zn(II)‐Stabilized Azo‐Anion Radical Catalyzed Sustainable C−C Bond Formation: Regioselective Alkylation of Fluorene, Oxindole, and Indoles

ChemCatChem, Год журнала: 2024, Номер 16(10)

Опубликована: Фев. 7, 2024

Abstract Herein we report a sustainable approach for the alkylation of ketones, 9 H ‐fluorene, oxindole, and indole using alcohols as alkylating agent catalyzed by well‐defined air‐stable zinc catalyst ( 1 ) tridentate redox non‐innocent arylazo ligand, 2‐((4‐chlorophenyl)diazenyl)‐1,10‐phenanthroline L ). 2–3 mol % efficiently produces substituted α‐alkylated 9‐alkylated fluorenes, C3 ‐alkylated oxindoles, indoles in moderate to good isolated yields. In aerial condition, formation bis(indolyl)methane (BIMs) derivatives were observed when subjected primary alcohols. A few drug molecules containing BIMs prepared The exhibited chemoselectivity during functionalization fluorene with oleyl alcohol β‐citronellol. control experiments, including deuterium labeling performed unveil reaction mechanism indicate that one‐electron reduced azo‐anion radical species [ ]‐formed situ, acts active catalyst. All events occur at redox‐active aryl‐azo which reservoir hydrogen electrons throughout catalytic cycle, keeping Zn(II)‐center template.

Язык: Английский

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Single-Molecular Mn(I)-Complex-Catalyzed Tandem Double Dehydrogenation Cross-Coupling of (Amino)Alcohols under Solventless Conditions with the Liberation of H₂ and H₂O

ACS Sustainable Chemistry & Engineering, Год журнала: 2022, Номер 10(22), С. 7362 - 7373

Опубликована: Май 24, 2022

Sustainable chemical production requires fundamentally new types of catalysts and catalytic technologies. The development coherent robust systems based on earth-abundant transition metals is essential but extremely challenging. Herein, we report the first a single Mn(I)-PNP catalyzed tandem C–C C–N bond formation via double dehydrogenative coupling amino alcohols with primary alcohols. current method covers wide range substrates, including aryl, aliphatic, acyclic, cyclic alcohols, as well to provide diverse N-heterocyclic compounds (pyridine quinoline derivatives) in good excellent yields (50 examples). reaction proceeds under benign, solventless conditions liberation molecular hydrogen water only byproducts. Various control labeling experiments kinetic, nuclear magnetic resonance, mechanistic studies suggest that operates acceptorless pathway, selectively assimilating desired N-heterocycles. Several selective activation/formation reactions occur sequentially amine–amide metal–ligand cooperation.

Язык: Английский

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Recent advances in C/N-alkylation with alcohols through hydride transfer strategies

Organic & Biomolecular Chemistry, Год журнала: 2022, Номер 20(39), С. 7713 - 7745

Опубликована: Янв. 1, 2022

Recent advances in C/N alkylation using alcohols as alkylating reagents via hydrogen-shuttle methodologies: Borrowing Hydrogen, Acceptorless Dehydrogenative Coupling, and Base-mediated Hydride Transfer.

Язык: Английский

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