Transition-metal catalyzed C–H activation as a means of synthesizing complex natural products

Chemical Society Reviews, Год журнала: 2023, Номер 52(21), С. 7461 - 7503

Опубликована: Янв. 1, 2023

Over the past few decades, advent of C–H activation has led to a rethink among chemists about synthetic strategies employed for multi-step transformations.

Язык: Английский

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Dual-Ligand Catalyst for the Nondirected C–H Olefination of Heteroarenes

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(14), С. 8198 - 8208

Опубликована: Март 28, 2023

Pd(II)-catalyzed nondirected C-H functionalization of heteroarenes is a significant challenge for the following reasons: poor reactivity electron-deficient heterocycles and unproductive coordination Lewis basic nitrogen atoms. Existing methodologies using palladium catalysis often employ large excess heterocycle substrates to overcome these hurdles. Despite recent advances in arenes that allow them be used as limiting reagents, reaction conditions are incompatible with heteroarenes. Herein we report dual-ligand catalyst enables olefination without substrate. In general, use 1-2 equiv was sufficient obtain synthetically useful yields. The rationalized by synergy between two types ligands: bidentate pyridine-pyridone ligand promotes cleavage; monodentate substrate acts second form cationic Pd(II) complex has high affinity arenes. proposed cooperation supported combination X-ray, kinetics, control experiments.

Язык: Английский

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Redox-neutral carbon–heteroatom bond formation under photoredox catalysis

Chemical Communications, Год журнала: 2023, Номер 59(46), С. 7004 - 7027

Опубликована: Янв. 1, 2023

This feature article presents all the recent reports on photoredox-catalyzed redox-neutral carbon–heteroatom coupling reactions up to March 2023.

Язык: Английский

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Controlling Reactivity and Selectivity in the Nondirected C–H Activation of Arenes with Palladium

Accounts of Chemical Research, Год журнала: 2023, Номер 56(18), С. 2459 - 2472

Опубликована: Авг. 24, 2023

ConspectusAromatic structures are widespread motifs throughout organic chemistry, and C-H activation has been recognized as a major tool for enabling their sustainable efficient functionalization. Through activation, arenes can be modified without the need prefunctionalization, leading to inherent atom- step-economic advantages over traditional methods. However, development of synthetically useful methods, several hurdles have overcome. The strength bonds necessitates sufficiently reactive catalysts, while presence multiple within substrate poses challenges in terms site-selectivity. Traditionally these addressed by control. By attaching different directing groups (DGs), reactivity respective arene was significantly enhanced DG guided metal close proximity specific bonds, resulting high introduction removal add additional steps synthetic sequence, scope reaction is limited class. complementary nondirected methods that applied broad range necessity carry functional group coordinates Pd (referred simple arenes) therefore highly desirable. intrinsically lower such substrates absence selectivity-determining pose significant solved only catalysts. Consequently, field especially with respect Pd-catalyzed remained comparatively underdeveloped when we initiated our research program 2017. At time, state-of-the-art required used large excess, precluding its use late-stage Since organopalladium species among most versatile intermediates, realized developing system, which effectively selectively activate limiting reagent, would powerful chemistry. This account summarizes groups' toward application catalytic systems offering this desired focuses explicitly on functionalization reactions arenes, where employed reagent. After an state before 2017 associated challenges, experimental mechanistic details about first arene-limited, palladium will discussed. enabled identification combination two ligands, N-heterocycle amino acid-derived ligand. Afterward discuss expansion dual-ligand approach further arene-limited transformations. Finally, describe methodologies originated from observations made during studies, namely, deuteration selective olefination method uses noncovalent interactions induce meta selectivity.

Язык: Английский

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Metal-free photoinduced hydrogen atom transfer assisted C(sp³)–H thioarylation

Green Chemistry, Год журнала: 2023, Номер 25(9), С. 3431 - 3436

Опубликована: Янв. 1, 2023

A mild metal-free approach for C(sp 3 )–H thioarylation of organic building blocks.

Язык: Английский

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Accelerating explicit solvent models of heterogeneous catalysts with machine learning interatomic potentials

Chemical Science, Год журнала: 2023, Номер 14(31), С. 8338 - 8354

Опубликована: Янв. 1, 2023

Realistically modelling how solvents affect catalytic reactions is a longstanding challenge due to its prohibitive computational cost. Typically, an explicit atomistic treatment of the solvent molecules needed together with molecular dynamics (MD) simulations and enhanced sampling methods. Here, we demonstrate utility machine learning interatomic potentials (MLIPs), coupled active learning, enable fast accurate adsorption on heterogeneous catalysts. MLIPs trained on-the-fly were able accelerate ab initio MD by up 4 orders magnitude while reproducing high fidelity geometrical features water in bulk at metal-water interfaces. Using these ML-accelerated simulations, accurately predicted key quantities such as energies CO*, OH*, COH*, HCO*, OCCHO* Cu surfaces free energy barriers C-H scission ethylene glycol over Pd surfaces, validated calculations. We envision that will pave way towards detailed realistic studies solvated catalysts large time- length-scales.

Язык: Английский

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Deuteration and Tritiation of Pharmaceuticals by Non‐Directed Palladium‐Catalyzed C–H Activation in Heavy and Super‐Heavy Water

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(48)

Опубликована: Авг. 7, 2024

Abstract Deuterated and tritiated analogs of drugs are valuable compounds for pharmaceutical medicinal chemistry. In this work, we present a novel hydrogen isotope exchange reaction using non‐directed homogeneous Pd‐catalysis. Aromatic C−H activation is achieved by commercially available pyridine ligand. Using the most convenient cheapest deuterium source, D 2 O, as only solvent 39 pharmaceuticals were labelled with clean profiles high uptakes. Additionally, describe first application Pd‐catalysis H/T on three different T O isotopic demonstrating applicability to synthesis radiotracers.

Язык: Английский

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Advancing Heterogeneous Organic Synthesis With Coordination Chemistry‐Empowered Single‐Atom Catalysts

Advanced Materials, Год журнала: 2024, Номер unknown

Опубликована: Сен. 18, 2024

Abstract For traditional metal complexes, intricate chemistry is required to acquire appropriate ligands for controlling the electron and steric hindrance of active centers. Comparatively, preparation single‐atom catalysts much easier with more straightforward effective accesses arrangement control The presence coordination atoms or neighboring functional on supports' surface ensures stability single‐atoms their interactions individual substantially regulate performance Therefore, collaborative interaction between surrounding environment enhances initiation reaction substrates formation transformation crucial intermediate compounds, which imparts significant catalytic efficacy, rendering them a valuable framework investigating correlation structure activity, as well mechanism in organic reactions. Herein, comprehensive overviews both homogeneous complexes reactions are provided. Additionally, reflective conjectures about advancement synthesis also proposed present reference later development.

Язык: Английский

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Chemodivergent Chalcogenation of Aryl Alkynoates or N-Arylpropynamides Using 9-Mesityl-10-Methylacridinium Perchlorate Photocatalyst

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(14), С. 10096 - 10110

Опубликована: Июль 3, 2023

Herein we report a cascaded chalcogenation of aryl alkynoates or N-arylpropynamides using 9-mesityl-10-methylacridinium perchlorate as visible light photocatalyst to obtain selectively either 3-sulfenylated/selenylated coumarins spiro[4,5]trienones. In radical initiated process, the spiro-cyclization reaction was favored due presence -OMe -F substituent at para position group, which helped stabilize allylic intermediate formed during reaction. Otherwise, 6-endo-trig cyclization led coumarins. Overall, new C–S/C–Se, C–C, and C═O bonds were in single step. The Stern–Volmer quenching study, EPR experiments, ON-OFF trapping etc., understand radical-based mechanism.

Язык: Английский

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Transition Metal‐Catalyzed C−H Functionalization Through Electrocatalysis

ChemSusChem, Год журнала: 2023, Номер 16(12)

Опубликована: Март 7, 2023

Electrochemically promoted transition metal-catalyzed C-H functionalization has emerged as a promising area of research over the last few decades. However, development in this field is still at an early stage compared to traditional reactions using chemical-based oxidizing agents. Recent reports have shown increased attention on electrochemically functionalization. From standpoint sustainability, environmental friendliness, and cost effectiveness, oxidation metal catalyst offers mild, efficient, atom-economical alternative chemical oxidants. This Review discusses advances metal-electrocatalyzed past decade describes how unique features electricity enable economic sustainable way.

Язык: Английский

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