3d Transition Metals for C–H Activation

Chemical Reviews, Год журнала: 2018, Номер 119(4), С. 2192 - 2452

Опубликована: Ноя. 27, 2018

C–H activation has surfaced as an increasingly powerful tool for molecular sciences, with notable applications to material crop protection, drug discovery, and pharmaceutical industries, among others. Despite major advances, the vast majority of these functionalizations required precious 4d or 5d transition metal catalysts. Given cost-effective sustainable nature earth-abundant first row metals, development less toxic, inexpensive 3d catalysts gained considerable recent momentum a significantly more environmentally-benign economically-attractive alternative. Herein, we provide comprehensive overview on until summer 2018.

Язык: Английский

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Visible Light-Driven Radical-Mediated C–C Bond Cleavage/Functionalization in Organic Synthesis

Chemical Reviews, Год журнала: 2020, Номер 121(1), С. 506 - 561

Опубликована: Май 29, 2020

Thermal C–C bond cleavage reactions allow the construction of structurally diverse molecular skeletons via predictable and efficient reorganizations. Visible light photoredox-catalyzed radical-mediated have recently emerged as a powerful alternative method for overcoming thermodynamic kinetic barrier in scaffolds. In recent years, plethora elegant useful been invented, products are sometimes otherwise inaccessible by classic thermal reactions. Considering great influence synthetic potential these reactions, we provide summary state art visible light-driven cleavage/functionalization strategies with specific emphasis on working models. We hoped that this review will be medicinal organic chemists inspire further reaction development interesting area.

Язык: Английский

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Cleavage of carbon–carbon bonds by radical reactions

Chemical Society Reviews, Год журнала: 2019, Номер 48(9), С. 2615 - 2656

Опубликована: Янв. 1, 2019

This review provides insights into thein situgenerated radicals triggered carbon–carbon bond cleavage reactions.

Язык: Английский

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Radical-Mediated Remote Functional Group Migration

Accounts of Chemical Research, Год журнала: 2020, Номер 53(8), С. 1620 - 1636

Опубликована: Июль 24, 2020

ConspectusAlkenes are ubiquitous in natural products and extensively used as synthetic feedstocks multiple fields including organic synthesis, medicinal chemistry, materials science. Radical-mediated difunctionalization of alkenes provides a powerful tactic for alkene utilization. Despite the considerable progress made past several decades, state-of-the-art methods highly dependent upon activated which proximal group with π-electron system (e.g., aryl, carbonyl, heteroatom) is requisite to stabilize nascent alkyl radical intermediate via p−π conjugation or p orbitals heteroatom. In contrast, transformation unactivated alkenes, such aliphatic remains challenging.To overcome this obstacle, we have recently disclosed strategy intramolecular distal functional migration (FGM), has been efficiently applied alkenes. A portfolio groups, cyano, heteroaryl, oximino, formyl, alkynyl showcase excellent migratory aptitude. Mechanistically, after addition an extrinsic alkene, newly formed active rapidly captured by generate cyclic intermediate. Subsequent cleavage C–C bond leads functionalized product through FGM process. Based on FGM, set elusive difunctionalizations accomplished (Part A).Alongside research, upgraded efficient strategy, "dock-migration," created intermolecular diversity sulfone-based dual-function reagents developed. The initiated docking reagent followed group. Compared original protocol, scope significantly extended from strategically placed tertiary alcohol-substituted general Both well tolerated. By approach, radical-mediated fluoroalkylheteroarylation, fluoroalkylalkynylation, alkylation achieved B).Direct elaboration C–H bonds into targeted groups represents one most ideal straightforward molecular functionalization. proves be ingenious tool functionalization remote C(sp3)–H bonds. process, accomplished: (a) heteroarylation cyanation unprotected alcohols cascade alkoxy radical-enabled hydrogen atom transfer (HAT) cyano) migration, (b) vinylation propargylic consecutive alkenyl radical-promoted HAT process subsequent C).

Язык: Английский

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A general deoxygenation approach for synthesis of ketones from aromatic carboxylic acids and alkenes

Nature Communications, Год журнала: 2018, Номер 9(1)

Опубликована: Авг. 23, 2018

Abstract The construction of an aryl ketone structural unit by means catalytic carbon–carbon coupling reactions represents the state-of-the-art in organic chemistry. Herein we achieved direct deoxygenative synthesis aqueous solution from readily available aromatic carboxylic acids and alkenes, affording structurally diverse ketones moderate to good yields. Visible-light photoredox catalysis enables deoxygenation as acyl sources with triphenylphosphine a distinct perspective on activation. synthetic robustness is supported late-stage modification several pharmaceutical compounds complex molecules. This strategy further applied drug zolpidem three steps 50% total yield concise cyclophane-braced 18–20 membered macrocycloketones. It not only advancement for streamlined feedstock chemicals, but also radical activation mode beyond redox potential acids.

Язык: Английский

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Radical-mediated rearrangements: past, present, and future

Chemical Society Reviews, Год журнала: 2021, Номер 50(20), С. 11577 - 11613

Опубликована: Янв. 1, 2021

This Review summarizes the past to present achievements in radical-mediated rearrangements, and brings up prospects that may inspire colleagues develop more useful synthetic tools based on radical rearrangements.

Язык: Английский

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Deoxygenative Deuteration of Carboxylic Acids with D₂O

Angewandte Chemie International Edition, Год журнала: 2018, Номер 58(1), С. 312 - 316

Опубликована: Окт. 23, 2018

We report a general, practical, and scalable means of preparing deuterated aldehydes from aromatic aliphatic carboxylic acids with D2 O as an inexpensive deuterium source. The use Ph3 P O-atom transfer reagent can facilitate the deoxygenation acids, while Ph2 POEt is better for acids. highly precise complex makes this protocol promising late-stage deoxygenative deuteration natural product derivatives pharmaceutical compounds.

Язык: Английский

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Organic Electrosynthesis: Applications in Complex Molecule Synthesis

ChemElectroChem, Год журнала: 2019, Номер 6(16), С. 4067 - 4092

Опубликована: Май 23, 2019

Abstract Organic electrosynthesis is an enabling and sustainable technology, which constitutes a rapidly expanding field of research. Electrochemical approaches serve as convenient green alternatives to stoichiometric toxic chemical redox agents. Electrosynthesis promising platform for harnessing the unique reactivity profiles radical intermediates, expediting development new reaction manifolds. This Review highlights both anodic cathodic methods construction various kinds complex molecules.

Язык: Английский

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Visible light-promoted ring-opening functionalization of three-membered carbo- and heterocycles

Chemical Society Reviews, Год журнала: 2020, Номер 49(9), С. 2546 - 2556

Опубликована: Янв. 1, 2020

In this tutorial review, synthetic and mechanistic aspects of visible light-promoted ring-opening functionalization three-membered carbo- heterocycles are highlighted.

Язык: Английский

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Desulfonylation via Radical Process: Recent Developments in Organic Synthesis

Chemical Reviews, Год журнала: 2021, Номер 121(20), С. 12548 - 12680

Опубликована: Авг. 13, 2021

As the "chemical chameleon", sulfonyl-containing compounds and their variants have been merged with various types of reactions for efficient construction diverse molecular architectures by taking advantage incredible reactive flexibility. Currently, involvement in radical transformations, which sulfonyl group typically acts as a leaving via selective C–S, N–S, O–S, S–S, Se–S bond cleavage/functionalization, has facilitated new formation strategies are complementary to classical two-electron cross-couplings organometallic or ionic intermediates. Considering great influence synthetic potential these novel avenues, we summarize recent advances this rapidly expanding area discussing reaction designs, substrate scopes, mechanistic studies, limitations, outlining state-of-the-art processes involved radical-mediated desulfonylation related transformations. With specific emphasis on applications, believe review will be useful medicinal organic chemists who interested chemistry particular.

Язык: Английский

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