Borrowing Hydrogen for Organic Synthesis

ACS Central Science, Journal Year: 2021, Volume and Issue: 7(4), P. 570 - 585

Published: March 25, 2021

Borrowing hydrogen is a process that used to diversify the synthetic utility of commodity alcohols. A catalyst first oxidizes an alcohol by removing form reactive carbonyl compound. This intermediate can undergo diverse range subsequent transformations before returns "borrowed" liberate product and regenerate catalyst. In this way, alcohols may be as alkylating agents whereby sole byproduct one-pot reaction water. recent decades, significant advances have been made in area, demonstrating many effective methods access valuable products. outlook highlights diversity metal biocatalysts are available for approach, well various performed, focusing on selection most advances. By succinctly describing conveying versatility borrowing chemistry, we anticipate its uptake will increase across wider scientific audience, expanding opportunities further development.

Language: Английский

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

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(9), P. 6078 - 6144

Published: April 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

Language: Английский

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Harnessing alcohols as sustainable reagents for late-stage functionalisation: synthesis of drugs and bio-inspired compounds

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(9), P. 4607 - 4647

Published: Jan. 1, 2024

This review collectively discussed the utilisation of alcohols in various organic transformations and their application toward intermediates drugs, drug derivatives natural product-like molecules.

Language: Английский

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Recent advances in the synthesis and reactivity of quinoxaline

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 8(11), P. 2820 - 2862

Published: Jan. 1, 2021

Quinoxalines are observed in several bioactive molecules and have been widely employed designing for DSSC's, optoelectronics, sensing applications. Therefore, developing newer synthetic routes as well novel ways their functionalization is apparent.

Language: Английский

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Cobalt-catalyzed chemoselective alkenylation and alkylation of C(sp3)–H bond in methyl heteroarenes

Journal of Catalysis, Journal Year: 2024, Volume and Issue: 435, P. 115569 - 115569

Published: May 25, 2024

Language: Английский

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Rhodium-Catalyzed C–H Annulation of Free Anilines with Vinylene Carbonate as a Bifunctional Synthon

Organic Letters, Journal Year: 2021, Volume and Issue: 23(22), P. 8910 - 8915

Published: Nov. 10, 2021

Chemical transformation with vinylene carbonate as an emerging synthetic unit has recently attracted considerable attention. This report is a novel conversion pattern carbonate, in which such vibrant reagent unprecedentedly acts difunctional coupling partner to complete the C-H annulation of free anilines. From commercially available substrates, this protocol leads rapid construction synthetically versatile 2-methylquinoline derivatives (43 examples) excellent functionality tolerance.

Language: Английский

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Copper-Mediated C4-Benzylations of 5-Aminopyrazoles with 3-Indoleacetic Acids

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(11), P. 6623 - 6632

Published: May 11, 2023

Herein, we present a copper-mediated C4-benzylation of 5-aminopyrazoles with 3-indoleacetic acids. Various benzylated are prepared in good-to-excellent yields under basic and ligand-free conditions the presence copper acetate. Moreover, this benzylation method is applicable to other substrates, including naphthylamine, 2-aminochromen-4-one, enamines. Some products exhibit antiproliferative activities against cancer cell lines. In addition, C4-benzylated cyclized into 1H-pyrazolo[4',3':6,7]azepino[3,4-b]indoles aldehydes via one-pot two-step processes; notably, fluorescence emissions large Stokes shifts.

Language: Английский

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Recent advances on non-precious metal-catalyzed C–H functionalization of N-heteroarenes

Chemical Communications, Journal Year: 2021, Volume and Issue: 58(1), P. 10 - 28

Published: Nov. 18, 2021

N-Heteroarenes are widely used for numerous medicinal applications, lifesaving drugs and show utmost importance as intermediates in chemical synthesis. This feature article highlights the recent advances, from 2015 to August 2021, on sp2 sp3 C-H bond functionalization reactions of various N-heteroarenes catalyzed by non-precious transition metals (Mn, Co, Fe, Ni, etc.). The salient features report are: (i) development newer catalysis Csp2-H activation categorized into alkylation, alkenylation, borylation, cyanation, annulation reactions, (ii) advances Csp3-H considering approaches alkylation well alkenylation processes, (iii) synthetic applications practical utility catalytic protocols utilized late-stage drug development; (iv) scope along with mechanistic studies detail findings important processes.

Language: Английский

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

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(7), P. 1531 - 1537

Published: Jan. 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.

Language: Английский

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Atom‐Economic Alk(en)ylations of Esters, Amides, and Methyl Heteroarenes Utilizing Alcohols Following Dehydrogenative Strategies

Asian Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 10(3), P. 464 - 484

Published: Jan. 19, 2021

Abstract Owing to the atom‐economic and greener nature, borrowing hydrogen (BH) acceptorless dehydrogenative coupling (ADC) processes have drawn significant attentions of researchers across globe thus, these strategies been extensively utilized in synthetic chemistry access various challenging valuable compounds. During last decade, progress has witnessed utilization protocols involving alkylation amides/esters/N‐heteroarenes by replacing traditionally mutagenic reagents as alkyl source with sustainable biomass derived alcohols under BH/ADC process. This includes mainly transition metal based catalytic systems although a few metal‐free are reported. In this minireview, advancement from 2010 until September 2020 accessing C‐alk(en)ylated compounds unactivated utilizing via strategy is highlighted. Additionally, reports on aldehydes instead partners also discussed.

Language: Английский

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