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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Manganese(I)-Catalyzed Sustainable Synthesis of Quinoxaline and Quinazoline Derivatives with the Liberation of Dihydrogen

The Journal of Organic Chemistry, Journal Year: 2020, Volume and Issue: 85(11), P. 7181 - 7191

Published: May 13, 2020

Direct synthesis of N-heterocycles via the acceptorless dehydrogenative coupling is very challenging and scarcely reported under 3d transition-metal catalysis. Here, we have developed an efficient Mn(I)-catalyzed sustainable various quinoxalines from 1,2-diaminobenzenes 1,2-diols reaction. Further, this strategy was successfully applied for unprecedented quinazolines by reaction 2-aminobenzyl alcohol with primary amides. The present protocol provides atom-economical route quinoxaline quinazoline derivatives employing earth-abundant manganese salt simple phosphine-free NNN-tridentate ligand.

Language: Английский

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Recent advances in nickel-catalyzed C–C and C–N bond formation via HA and ADC reactions

Organic & Biomolecular Chemistry, Journal Year: 2021, Volume and Issue: 19(19), P. 4213 - 4227

Published: Jan. 1, 2021

In this review article, recent advances in nickel-catalyzed hydrogen auto-transfer (HA) and acceptorless dehydrogenative coupling (ADC) reactions for the construction of C–C C–N bonds have been discussed.

Language: Английский

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Recent advances on cross-coupling of alcohols via borrowing hydrogen catalysis

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(30), P. 4002 - 4014

Published: Jan. 1, 2024

This article highlights the recent advances and significance of β-alkylation reactions towards synthesis higher order alcohols.

Language: Английский

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Reaction condition controlled nickel(ii)-catalyzed C–C cross-coupling of alcohols

Organic & Biomolecular Chemistry, Journal Year: 2019, Volume and Issue: 17(14), P. 3567 - 3574

Published: Jan. 1, 2019

The challenge in the C-C cross-coupling of secondary and primary alcohols using acceptorless dehydrogenation coupling (ADC) is difficulty accurately controlling product selectivities. Herein, we report a controlled approach to diverse range β-alkylated alcohols, α-alkylated ketones α,β-unsaturated ADC methodology employing Ni(ii) 4,6-dimethylpyrimidine-2-thiolate cluster catalyst under different reaction conditions. This could tolerate wide substrates exhibited high activity for annulation with 2-aminobenzyl yield quinolines. work an example precise chemoselectivity control by careful choice

Language: Английский

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General Synthesis of N-Alkylation of Amines with Secondary Alcohols via Hydrogen Autotransfer

Organic Letters, Journal Year: 2019, Volume and Issue: 21(22), P. 8899 - 8903

Published: Nov. 6, 2019

Direct catalytic N-alkylation of amines with secondary alcohols via hydrogen autotransfer (HA) strategy is very challenging and has been scarcely reported, even under precious metal catalysis. Herein, an efficient amines, including benzylamines using as alkylating agents, reported. This reaction catalyzed by a molecularly defined NNN-Ni(II) pincer complex, the operates mild, benign conditions. Various substrates functional groups were tolerated. Preliminary mechanistic studies suggest that proceeds mechanism.

Language: Английский

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Nickel-Catalyzed Direct Synthesis of Quinoxalines from 2-Nitroanilines and Vicinal Diols: Identifying Nature of the Active Catalyst

The Journal of Organic Chemistry, Journal Year: 2020, Volume and Issue: 85(4), P. 2775 - 2784

Published: Jan. 6, 2020

The inexpensive and simple NiBr2/1,10-phenanthroline system-catalyzed synthesis of a series quinoxalines from both 2-nitroanilines 1,2-diamines is demonstrated. reusability test for this system was performed up to the seventh cycle, which afforded good yields desired product without losing its reactivity significantly. Notably, during catalytic reaction, formation heterogeneous Ni-particle observed, characterized by PXRD, XPS, TEM techniques.

Language: Английский

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Iron‐Catalyzed Borrowing Hydrogen C‐Alkylation of Oxindoles with Alcohols

ChemSusChem, Journal Year: 2019, Volume and Issue: 12(11), P. 2345 - 2349

Published: April 8, 2019

A general and efficient iron-catalyzed C-alkylation of oxindoles has been developed. This borrowing hydrogen approach employing a (cyclopentadienone)iron carbonyl complex (2 mol %) exhibited broad reaction scope, allowing benzylic simple primary secondary aliphatic alcohols to be employed as alkylating agents. variety underwent selective mono-C3-alkylation in good-to-excellent isolated yields (28 examples, 50-92 % yield, 79 average yield).

Language: Английский

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Sustainable and Selective Alkylation of Deactivated Secondary Alcohols to Ketones by Non‐bifunctional Pincer N‐heterocyclic Carbene Manganese

ChemSusChem, Journal Year: 2020, Volume and Issue: 13(10), P. 2557 - 2563

Published: March 31, 2020

Abstract A sustainable and green route to access diverse functionalized ketones via dehydrogenative–dehydrative cross‐coupling of primary secondary alcohols is demonstrated. This borrowing hydrogen approach employing a pincer N‐heterocyclic carbene Mn complex displays high activity selectivity. variety are well tolerant result in satisfactory isolated yields. Mechanistic studies suggest that this reaction proceeds direct outer‐sphere mechanism the dehydrogenation alcohol substrates plays vital role rate‐limiting step.

Language: Английский

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