Merging Photoinduced Iron-Catalyzed Decarboxylation with Copper Catalysis for C–N and C–C Couplings

ACS Catalysis, Год журнала: 2023, Номер 13(3), С. 1678 - 1685

Опубликована: Янв. 13, 2023

We report a photoinduced iron/copper dual-catalytic strategy for the radical decarboxylation functionalization of aliphatic carboxylic acids. The ligand-to-iron charge transfer process under light was initially occurred to generate an unstabilized alkyl radical, and copper catalyst delivered enabled subsequent coupling reactions form C–N or C–C bonds. By merging iron-catalyzed with catalysis, this system allows smooth conversion wide range acids amination, decarboxylative dehydrogenation, alkylation efficiently. A variety complex drug natural molecules is applicable, suggesting that would facilitate rapid compound library synthesis benefit discovery pharmaceutical agents.

Язык: Английский

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Contemporary Approaches for Amide Bond Formation

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(24), С. 4359 - 4391

Опубликована: Ноя. 7, 2023

Abstract Amide bond construction has garnered significant interest in recent decades due to amides being one of the most prevalent functional groups among bioactive molecules. Out thirty‐seven new drugs approved by FDA 2022, eleven are small molecules containing at least amide bond. Additionally, there nineteen large as drugs, some which have peptide structures, and therefore, also bear bonds. In years, multiple teams embraced challenge developing more efficient methods for formation. This dedication led numerous publications appearing monthly prestigious journals, showcasing advancements this field. The primary goal review is present viable strategies constructing It crucial differentiate between formation synthesis; hence, focus on describing specific forming C(O)−N particular, concentrates developed within last six years. There a particular emphasis approaches that consider thought process when selecting starting materials groups. approach ensures coverage all common chemical transformations yield

Язык: Английский

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Nitrogen Atom Transfer Catalysis by Metallonitrene C−H Insertion: Photocatalytic Amidation of Aldehydes

Angewandte Chemie International Edition, Год журнала: 2021, Номер 61(9)

Опубликована: Дек. 14, 2021

C-H amination and amidation by catalytic nitrene transfer are well-established typically proceed via electrophilic attack of nitrenoid intermediates. In contrast, the insertion (formal) terminal nitride ligands into bonds is much less developed nitrogen atom remains unknown. We here report synthesis a formal complex palladium. Photocrystallographic, magnetic, computational characterization support assignment as an authentic metallonitrene (Pd-N) with diradical ligand that singly bonded to Pd

Язык: Английский

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Adaptive Catalytic Systems for Chemical Energy Conversion

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(33)

Опубликована: Июнь 22, 2023

Abstract The rapidly growing importance of green hydrogen and renewable carbon resources as essential feedstocks for sustainable chemical value chains opens room disruptive innovations regarding production processes. fluctuation variability associated with non‐fossil energy raw material supply holds many challenges catalysts to cope the resulting dynamics. However, new opportunities also arise once catalyst design starts aim at performance that is “adaptive” rather than “task‐specific”. In this Scientific Perspective, we propose define adaptivity in catalysis on basis three properties are reversibility, rapidity, robustness ( R 3 rule). Promising strategies selected examples described substantiate scientific concept highlight its potential conversion.

Язык: Английский

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Mild Amide Synthesis Using Nitrobenzene under Neutral Conditions

Organic Letters, Год журнала: 2022, Номер 24(26), С. 4766 - 4771

Опубликована: Июнь 27, 2022

Amide synthesis is one of the most important transformations in organic chemistry due to broad application pharmaceutical drugs and materials. In this report, we describe a mild protocol for amide formation using readily available nitroarenes as nitrogen sources an inexpensive iron complex catalyst. Because use pH-neutral conditions avoidance strong oxidant or reductant, wide range aromatic aliphatic aldehydes well with various functional groups could be tolerated well. A plausible mechanism proposed based on detailed studies, which catalyst initiates radical process solvent plays key role O-atom acceptor.

Язык: Английский

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Reduction of Carboxylic Acids to Alcohols via Manganese(I) Catalyzed Hydrosilylation

JACS Au, Год журнала: 2021, Номер 1(6), С. 742 - 749

Опубликована: Май 11, 2021

The reduction of carboxylic acids to the respective alcohols, in mild conditions, was achieved using [MnBr(CO)5] as catalyst and bench stable PhSiH3 reducing agent. It shown that reaction with earth-abundant metal could be performed either a loading low 0.5 mol %, rare use [MnBr(CO)5], or on gram scale employing only 1.5 equiv PhSiH3, lowest amount silane reported date for this transformation. Kinetic data control experiments have provided initial insight into mechanism catalytic process, suggesting it proceeds via formation silyl ester intermediates ligand dissociation generate coordinatively unsaturated Mn(I) complex active species.

Язык: Английский

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An Adaptive Rhodium Catalyst to Control the Hydrogenation Network of Nitroarenes

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(36)

Опубликована: Июнь 27, 2022

An adaptive catalytic system that provides control over the nitroarene hydrogenation network to prepare a wide range of aniline and hydroxylamine derivatives is presented. This takes advantage delicate interplay between rhodium(III) center Lewis acidic borane introduced in secondary coordination sphere metal. The high chemoselectivity catalyst presence various potentially vulnerable functional groups its readiness be deployed at preparative scale illustrate practicality. Mechanistic studies density theory (DFT) methods were used shed light on mode functioning elucidate origin adaptivity. competition for interaction with boron solvent molecule substrate was found crucial When operating THF, reduction stops platform, whereas reaction can directed platform toluene.

Язык: Английский

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Ammonia surrogates in the synthesis of primary amines

Organic & Biomolecular Chemistry, Год журнала: 2023, Номер 21(35), С. 7036 - 7051

Опубликована: Янв. 1, 2023

This review provides a comprehensive summary of the utilization ammonia replacements in synthesizing protected and free primary amines, encompassing both traditional reagents latest developments.

Язык: Английский

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Copper-Catalyzed One-Pot Synthesis of Quinazolinones from 2-Nitrobenzaldehydes with Aldehydes: Application toward the Synthesis of Natural Products

The Journal of Organic Chemistry, Год журнала: 2021, Номер 86(24), С. 18067 - 18080

Опубликована: Ноя. 23, 2021

A novel, efficient, and atom-economical approach for the construction of quinazolinones from 2-nitrobenzaldehydes has been unveiled via copper-catalyzed nitrile formation, hydrolysis, reduction in one pot first time. In this reaction, urea is used as a source nitrogen hydrazine hydrate both nitro group hydrolysis nitrile, atmospheric oxygen sole oxidant. The method portrays wide substrate scope with good functional tolerances. Moreover, was applied synthesis schizocommunin, tryptanthrin, phaitanthrin-A, phaitanthrin-B, 8H-quinazolino[4,3-b]quinazolin-8-one.

Язык: Английский

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Controlling Chemoselectivity of Catalytic Hydroboration with Light

Angewandte Chemie International Edition, Год журнала: 2021, Номер 61(8)

Опубликована: Дек. 14, 2021

The ability to selectively react one functional group in the presence of another underpins efficient reaction sequences. Despite many designer catalytic systems being reported for hydroboration reactions, which allow introduction a handle cross-coupling or act as mild method reducing polar functionality, these platforms rarely deal with more complex where multiple potentially reactive sites exist. Here we demonstrate, first time, use light distinguish between ketones and carboxylic acids molecules. By taking advantage different activation modes, single system can be used hydroboration, chemoselectivity dictated only by absence visible light.

Язык: Английский

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