Mechanochemical C−X/C−H Functionalization: An Alternative Strategic Access to Pharmaceuticals

European Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 2022(8)

Published: Jan. 11, 2022

Abstract In the pursuit of clean pharmaceutical production, chemists in medicinal industry require access to new sustainable methodologies reduce and even eliminate pollution, which is mainly produced by overuse organic solvents during chemical synthesis active ingredients (APIs). this context, solvent‐free/less mechanochemical functionalization small molecules has gradually emerged as a powerful strategy for green modification APIs, bioactive compounds, functional materials. review, we present an overview C−X/C−H applications chemistry, involving cross‐coupling, cross‐dehydrogenative coupling, oxidative coupling (via C−H activation pathway), direct radical pathway) key steps preparation APIs compounds.

Language: Английский

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Metal–Organic Framework: An Emergent Catalyst in C–N Cross-Coupling Reactions

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 469, P. 214667 - 214667

Published: July 1, 2022

Language: Английский

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Ritter-type amination of C(sp3)-H bonds enabled by electrochemistry with SO42−

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: July 16, 2022

Abstract By merging electricity with sulfate, the Ritter-type amination of C(sp 3 )-H bonds is developed in an undivided cell under room temperature. This method features broad substrate generality (71 examples, up to 93% yields), high functional-group compatibility, facile scalability, excellent site-selectivity and mild conditions. Common alkanes electron-deficient alkylbenzenes are viable substrates. It also provides a straightforward protocol for incorporating C-deuterated acetylamino group into sites. Application synthesis or modification pharmaceuticals their derivatives gram-scale demonstrate practicability this method. Mechanistic experiments show that sulfate radical anion, formed by electrolysis served as hydrogen atom transfer agent provide alkyl intermediate. paves convenient flexible pathway realizing various synthetically useful transformations mediated anion generated via electrochemistry.

Language: Английский

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Photochemical Synthesis of Anilines via Ni-Catalyzed Coupling of Aryl Halides with Ammonium Salts

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(24), P. 15590 - 15599

Published: Dec. 5, 2022

Easy, efficient, and economic synthesis of anilines remains an important challenge in synthetic chemistry. In this study, a Ni(OAc)2-bipyridine complex is shown to readily catalyze the amination aryl halides with ammonium salts under direct excitation light, allowing broad array chlorides bromides be converted into corresponding primary (hetero)arylamines absence external photosensitizer. Late-stage modification drug molecules 15N-labeling amines are also demonstrated number examples. Photoinduced generation Ni(I)-bipyridine species believed key step reaction, enabling Ni(I)/Ni(III) cycle for catalytic turnover.

Language: Английский

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Comproportionation and disproportionation in nickel and copper complexes

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(19), P. 6601 - 6616

Published: Jan. 1, 2023

This review covers factors that contribute to comproportionation and disproportionation reactions in transition metal complexes provide insight into the importance of these electron transfer events Ni- Cu-catalyzed transformations.

Language: Английский

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Prospects and challenges for nitrogen-atom transfer catalysis

Nature Reviews Chemistry, Journal Year: 2023, Volume and Issue: 7(6), P. 424 - 438

Published: April 13, 2023

Language: Английский

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Intermolecular Enantioselective Benzylic C(sp³)−H Amination by Cationic Copper Catalysis**

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(24)

Published: April 14, 2023

Chiral benzylic amines are privileged motifs in pharmacologically active molecules. Intramolecular enantioselective radical C(sp3 )-H functionalization by hydrogen-atom transfer has emerged as a straightforward, powerful tool for the synthesis of chiral amines, but methods intermolecular amination remain elusive. Herein, we report cationic copper catalytic system with peroxide an oxidant. This mild, straightforward method can be used to transform array feedstock alkylarenes and amides into high enantioselectivities, it good functional group tolerance broad substrate scope. More importantly, synthesize bioactive molecules, including drugs. Preliminary mechanistic studies indicate that reaction involves radicals generated transfer.

Language: Английский

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Dual role of nitroarenes as electrophiles and arylamine surrogates in Buchwald–Hartwig-type coupling for C–N bond construction

Chemical Science, Journal Year: 2024, Volume and Issue: 15(10), P. 3552 - 3561

Published: Jan. 1, 2024

A reductive and denitrative amination of nitroarenes has been developed, allowing the highly selective synthesis various di- triarylamines. The protocol employed synthetically upstream as both electrophiles amine sources.

Language: Английский

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Amino‐λ³‐iodane‐Enabled Electrophilic Amination of Arylboronic Acid Derivatives

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(12)

Published: Jan. 26, 2024

Abstract In this report, we describe the use of amino‐λ 3 ‐iodanes in electrophilic amination arylboronic acids and boronates. Iodine(III) reagents with transferable amino groups, including one an NH 2 group, were synthesized used amination, allowing synthesis a wide range primary secondary (hetero)arylamines. Mechanistic studies by DFT calculations indicate that reaction proceeds through process from tetravalent borate complex B−N dative bond.

Language: Английский

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Enantioselective Chan–Lam S-arylation of sulfenamides

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(9), P. 1010 - 1020

Published: Sept. 9, 2024

Language: Английский

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