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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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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Modular assembly of arenes, ethylene and heteroarenes for the synthesis of 1,2-arylheteroaryl ethanes

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(10), P. 1705 - 1714

Published: June 27, 2024

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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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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Nickel(II)–N^ΛN^ΛO Pincer Type Complex-Catalyzed N-alkylation of Amines with Alcohols via the Hydrogen Autotransfer Reaction

The Journal of Organic Chemistry, Journal Year: 2020, Volume and Issue: 85(11), P. 7125 - 7135

Published: May 8, 2020

A highly sustainable catalytic protocol for the coupling of alcohols and amines selective monoalkylated using Ni(II)–NΛNΛO pincer type complexes through borrowing hydrogen methodology is described. An array Ni(II) catalysts (1–3) was synthesized characterized by various spectral analytical methods. Furthermore, distorted square planar geometry (1 2) substantiated with single crystal X-ray diffraction study. The inexpensive nickel-based displays a broad substrate scope N-alkylation aromatic heteroaromatic diverse range primary excellent yields up to 97%. present approach environmentally benign, which liberates water as sole byproduct. short synthesis drug intermediates such mepyramine chloropyramine illustrates utility protocol.

Language: Английский

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Nickel-Catalyzed Alkylation of Ketone Enolates: Synthesis of Monoselective Linear Ketones

The Journal of Organic Chemistry, Journal Year: 2018, Volume and Issue: 84(2), P. 769 - 779

Published: Dec. 14, 2018

Herein we have developed a Ni-catalyzed protocol for the synthesis of linear ketones. Aryl, alkyl, and heteroaryl ketones as well alcohols yielded monoselective in up to 90% yield. The catalytic was successfully applied gram-scale synthesis. For practical utility, applications steroid derivative, oleyl alcohol, naproxen alcohol were employed. Preliminary investigations involving isolation Ni intermediate defined Ni–H species series deuterium-labeling experiments performed.

Language: Английский

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Nickel-Catalyzed Direct Alkenylation of Methyl Heteroarenes with Primary Alcohols

The Journal of Organic Chemistry, Journal Year: 2019, Volume and Issue: 84(15), P. 9819 - 9825

Published: July 2, 2019

An efficient nickel-catalyzed acceptorless dehydrogenative coupling of methyl-substituted heteroarenes with primary alcohols is achieved using an in situ generated complex inexpensive NiBr2 and readily available 8-aminoquinoline picolinic amide ligand. The protocol operationally simple scalable furnishes a series high-value 2-alkenylheteroarenes good yields (up to 88%) exclusive E-selectivity. reaction proceeds the release water molecular hydrogen, which was analyzed through gas chromatography validate mechanism.

Language: Английский

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