C–H Activation: Toward Sustainability and Applications

ACS Central Science, Год журнала: 2021, Номер 7(2), С. 245 - 261

Опубликована: Фев. 2, 2021

Since the definition of "12 Principles Green Chemistry" more than 20 years ago, chemists have become increasingly mindful need to conserve natural resources and protect environment through judicious choice synthetic routes materials. The direct activation functionalization C–H bonds, bypassing intermediate functional group installation is, in abstracto, step atom economic, but numerous factors still hinder sustainability large-scale applications. In this Outlook, we highlight research areas seeking overcome challenges activation: pursuit abundant metal catalysts, avoidance static directing groups, replacement oxidants, introduction bioderived solvents. We close by examining progress made subfield aryl borylation from its origins, highly efficient precious Ir-based systems, emerging 3d catalysts. future growth field will depend on industrial uptake, thus urge researchers strive toward sustainable activation.

Язык: Английский

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Reactivity-Controlling Factors in Carboxylate-Assisted C–H Activation under 4d and 3d Transition Metal Catalysis

ACS Catalysis, Год журнала: 2020, Номер 10(18), С. 10551 - 10558

Опубликована: Авг. 17, 2020

Detailed density functional theory calculations provide valuable insight into reactivity-controlling factors in transition metal-catalyzed C–H activation by carboxylate assistance. The chelation-assisted of a variety arenes 3d and 4d metal complexes was analyzed means bond order analysis through (DFT) as well energy decomposition DLPNO–CCSD(T) calculations, thereby providing in-depth information on distinct electronic influences the key state demonstrating preferred base-assisted internal electrophilic substitution (BIES) rather than concerted metalation-deprotonation (CMD) pathway.

Язык: Английский

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Unlocking Diverse π-Bond Enrichment Frameworks by the Synthesis and Conversion of Boronated Phenyldiethynylethylenes

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(14), С. 10167 - 10176

Опубликована: Март 27, 2024

The π-bond enrichment frameworks not only serve as a crucial building block in organic synthesis but also assume pivotal role the fields of materials science, biomedicine, photochemistry, and other related disciplines owing to their distinctive structural characteristics. incorporation various substituents into C═C double bonds tetrasubstituted alkenes is currently highly significant research area. However, with diverse on poses challenge achieving stereoselectivity. Here, we reported an efficient convergent route Cu-catalyzed borylalkynylation both symmetrical unsymmetrical 1,3-diynes, B2pin2, acetylene bromide construction boronated phenyldiethynylethylene (BPDEE) derivatives excellent chemo-, stereo-, regioselectivities. BPDEE could transform novel π-conjugated gem-diphenyldiethynylethylene (DPDEE), vinylphenyldiethynylethylene (VPDEE), phenyltriethynylethylene (PTEE) by stepwise process, which provides flexible platform for complex that were difficult synthesize previous methods. initial optical characterization revealed synthesized molecules exhibited aggregation-induced emission (AIE) properties, further establishes groundwork future applications enriches advances field functional research.

Язык: Английский

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Manganese complex-catalysed α-alkylation of ketones with secondary alcohols enables the synthesis of β-branched carbonyl compounds

Chemical Communications, Год журнала: 2020, Номер 56(60), С. 8376 - 8379

Опубликована: Янв. 1, 2020

Herein, β-branched carbonyl compounds were synthesised via the α-alkylation of ketones with secondary alcohols under "borrowing hydrogen" catalysis. A wide range alcohols, including various cyclic, acyclic, symmetrical, and unsymmetrical have been successfully applied developed reaction conditions. manganese(i) complex bearing a phosphine-free multifunctional ligand catalysed produced water as sole byproduct.

Язык: Английский

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Catalytic Alkyne Dimerization without Noble Metals

ACS Catalysis, Год журнала: 2020, Номер 10(9), С. 4895 - 4905

Опубликована: Апрель 1, 2020

1,3-Enynes are core structures of various natural products or pharmaceuticals and broadly used synthons in organic synthesis. Metal-catalyzed alkyne dimerization is a desirable preparation method, due to its perfect atom economy the readily available substrates. Controlling regio- stereoselectivity remains challenge, competing formation head-to-tail (gem) head-to-head (E/Z) isomers. Although catalytic systems based on noble metals have been extensively studied, there has growing interest replace these with environmentally benign inexpensive alternatives. In this Perspective, we highlight recent advances dimerization, without use metals.

Язык: Английский

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Additive-Controlled Divergent Synthesis of Tetrasubstituted 1,3-Enynes and Alkynylated 3H-Pyrrolo[1,2-a]indol-3-ones via Rhodium Catalysis

Organic Letters, Год журнала: 2021, Номер 23(3), С. 727 - 733

Опубликована: Янв. 8, 2021

Herein, we report the additive-controlled divergent synthesis of tetrasubstituted 1,3-enynes and alkynylated 3H-pyrrolo[1,2-a]indol-3-ones through rhodium-catalyzed C-H alkenylation/DG migration [3+2] annulation, respectively. This protocol features rare directing group in 1,3-diyne-involved activation, excellent regio- stereoselectivity, monofunctionalization over difunctionalization, broad substrate scope, moderate to high yields, good functional compatibility, mild redox-neutral conditions.

Язык: Английский

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Recent advances and perspectives in manganese-catalyzed C–H activation

Catalysis Science & Technology, Год журнала: 2020, Номер 11(2), С. 444 - 458

Опубликована: Дек. 10, 2020

Manganese-catalyzed C–H activation has become an emerging area in organic chemistry. These efficient and eco-friendly manganese catalysed reactions provides new opportunities the field of synthetic

Язык: Английский

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Nickel-catalyzed site- and stereoselective reductive alkylalkynylation of alkynes

Chem, Год журнала: 2021, Номер 7(4), С. 993 - 1005

Опубликована: Янв. 20, 2021

Язык: Английский

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Homogeneous Manganese-Catalyzed Hydrofunctionalizations of Alkenes and Alkynes: Catalytic and Mechanistic Tendencies

ACS Omega, Год журнала: 2022, Номер 7(42), С. 37008 - 37038

Опубликована: Окт. 11, 2022

In recent years, many manganese-based homogeneous catalytic precursors have been developed as powerful alternatives in organic synthesis. Among these, the hydrofunctionalizations of unsaturated C–C bonds correspond to outstanding ways afford compounds with more versatile functional groups, which are commonly used building blocks production fine chemicals and feedstock for industrial field. Herein, we present an account Mn-catalyzed alkenes alkynes main objective finding mechanistic tendencies that could serve a platform works come.

Язык: Английский

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Traceless Bidentate Directing Group Assisted Cobalt-Catalyzed sp²-C–H Activation and [4 + 2]-Annulation Reaction with 1,3-Diynes

Organic Letters, Год журнала: 2020, Номер 22(19), С. 7480 - 7485

Опубликована: Сен. 16, 2020

An efficient cobalt-catalyzed [4 + 2] annulation of hydrazones and 1,3-diynes has been developed for the synthesis 3-alkynylated isoquinolines engaging 2-aminopyridine as a traceless bidentate directing group. The strategy successfully extended 3,3′-biisoquinoline moieties via both one-pot well sequential approaches. utilization group with an inexpensive earth-abundant cobalt-catalyst under operationally simple reaction conditions makes present transformation more valuable appealing.

Язык: Английский

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