Transition-metal-catalyzed C–H bond alkylation using olefins: recent advances and mechanistic aspects

Chemical Society Reviews, Год журнала: 2022, Номер 51(17), С. 7358 - 7426

Опубликована: Янв. 1, 2022

Transition metal catalysis has contributed immensely to C-C bond formation reactions over the last few decades, and alkylation is no exception. The superiority of such methodologies traditional evident from minimal reaction steps, shorter times, atom economy while also allowing control regio- stereo-selectivity. In particular, hydrocarbonation alkenes grabbed increased attention due its fundamental ability effectively selectively synthesise a wide range industrially pharmaceutically relevant moieties. This review attempts provide scientific viewpoint systematic analysis recent developments in transition-metal-catalyzed various C-H bonds using simple activated olefins. key features mechanistic studies involved these transformations are described briefly.

Язык: Английский

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Discovery of Organic Optoelectronic Materials Powered by Oxidative Ar–H/Ar–H Coupling

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(2), С. 1224 - 1243

Опубликована: Янв. 4, 2024

Efficient and streamlined synthetic methods that facilitate the rapid build-up of structurally diverse π-conjugated systems are paramount importance in quest for organic optoelectronic materials. Among these methods, transition-metal-catalyzed oxidative Ar–H/Ar–H coupling reactions between two (hetero)arenes have emerged as a concise effective approach generating wide array bi(hetero)aryl fused heteroaryl structures. This innovative bypasses challenges associated with substrate pre-activation processes, thereby allowing creation frameworks were previously beyond reach using conventional Ar–X/Ar–M reactions. These inherent advantages ushered new design patterns molecules deviate from traditional methods. ground-breaking enables transcendence limitations repetitive material structures, ultimately leading to discovery novel high-performance In this Perspective, we provide an overview recent advances development materials through utilization We introduce several notable strategies domain, covering both directed non-directed strategies, dual chelation-assisted strategy ortho-C–H arylation/cyclization strategy. Additionally, shed light on role advancement Finally, discuss current existing protocols offer insights into future prospects field.

Язык: Английский

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C–H bond functionalization by high-valent cobalt catalysis: current progress, challenges and future perspectives

Chemical Communications, Год журнала: 2021, Номер 57(83), С. 10827 - 10841

Опубликована: Янв. 1, 2021

Over the last decade, high-valent cobalt catalysis has earned a place in spotlight as valuable tool for C-H activation and functionalization. Since discovery of its unique reactivity, more attention been directed towards utilization an alternative to noble metal catalysts. In particular, Cp*Co(III) complexes, well simple Co(II) Co(III) salts combination with bidentate chelation assistance, have extensively used development novel transformations. this review, we demonstrated existing trends functionalization methodology using highlighted main challenges overcome, perspective directions, which need be further developed future.

Язык: Английский

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Emergence of Pyrimidine-Based meta-Directing Group: Journey from Weak to Strong Coordination in Diversifying meta-C–H Functionalization

Accounts of Chemical Research, Год журнала: 2022, Номер 55(3), С. 354 - 372

Опубликована: Янв. 12, 2022

C-H activation has emerged as a powerful transformative synthetic tool to construct complex molecular frameworks, which are ubiquitous in natural products, medicines, dyes, polymers, and many more. However, reactivity selectivity, arising from the inertness of bonds their overabundance organic molecules, two major fundamental challenges developing various carbon-carbon (C-C) carbon-heteroatom (C-X) bond formation reactions via technique. Functional groups with coordinating capacity transition metal catalysts, profoundly known directing (DGs), have shown great promise exerting selective activation, often called site-selective or regioselective transformation target molecule. Advent group (DG)-assisted strategies not only resolved selectivity issues but also offers unique solution rapid synthesis molecules convenient predictable manner. Our laboratory, this regard, is fascinated by prospect DG-assisted distal functionalization arenes, remotely located existing group. Notably, opposition proximal ortho-C-H proceeded an energetically favorable five- seven-membered metallacycle, remained formidable challenge it required large macrocyclic metallacycle. Therefore, designing suitable template that would maintain distance geometric relationship between appended auxiliary order ensure prolific delivery catalyst closest proximity targeted was key success. In Yu devised elegant "U-shaped" for first time execute meta-C-H recruiting cyano-based initial effort diversify scope using led us realize "cyano-based DGs" intrinsically limited weak ability, competitive binding mode (end-on vs side-on), incompatibility acidic basic reaction conditions. search robust auxiliary, we were intrigued possibility strongly ability pyrimidine quinoline-based DGs.In Account, describe our journey weakly DG pyrimidine-based achieve diverse electronically sterically unbiased arenes. While some functionalizations achieved finding conditions, others mechanistic understanding. development realm constrained short linkers, attached arene interest through 2-4 atoms. later studies, demonstrated can be attained even though 10-atoms away arene. More importantly, transient successfully utilized deliver olefination arenes situ imine formation, provided step-economic route activation.We hope Account will stimulate further design provide guiding platform future functionalization.

Язык: Английский

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Dual Ligand Enabled Nondirected C–H Chalcogenation of Arenes and Heteroarenes

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(27), С. 12032 - 12042

Опубликована: Июнь 27, 2022

Chalcogenide motifs are present as principal moieties in a vast array of natural products and complex molecules. Till date, the construction these chalcogen has been restricted to either use directing groups or employment large excess electronically activated arenes, typically employed cosolvent. Despite being highly effective, methods have their own limitations step economy deployment an amount arenes. Herein, we report evolution catalytic system employing arene-limited, nondirected thioarylation arenes heteroarenes using complimentary dual-ligand approach. The reaction is controlled by combination steric electronic factors, utilization suitable ligand enables generation on spectrum that generated classical methods. ligands remains imperative protocol with theoretical calculations pointing towards monoprotected amino acid crucial concerted metalation deprotonation (CMD) mechanism characteristic [5,6]-palladacyclic transition state, while pyridine moiety assists active catalyst species formation product release. Combined experimental computational mechanistic investigations point toward C–H activation both regio- rate-determining. Interestingly, oxidative addition diphenyl disulfide substrate found be unlikely, alternative transmetalation-like involving Pd–Ag heterometallic proposed operative.

Язык: Английский

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The green chemistry paradigm in modern organic synthesis

Russian Chemical Reviews, Год журнала: 2023, Номер 92(12), С. RCR5104 - RCR5104

Опубликована: Дек. 1, 2023

After the appearance of green chemistry concept, which was introduced in vocabulary early 1990s, its main statements have been continuously developed and modified. Currently, there are 10–12 cornerstones that should form basis for an ideal chemical process. This review analyzes accumulated experience achievements towards design products processes reduce or eliminate use generation hazardous substances. The presents views leading Russian scientists specializing various fields this subject, including homogeneous heterogeneous catalysis, fine basic organic synthesis, electrochemistry, polymer chemistry, based on bio-renewable feedstocks energetic compounds materials. A new approach to quantitative evaluation environmental friendliness by authors is described. <br> bibliography includes 1761.

Язык: Английский

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Distal meta-alkenylation of formal amines enabled by catalytic use of hydrogen-bonding anionic ligands

Chem, Год журнала: 2023, Номер 9(4), С. 989 - 1003

Опубликована: Янв. 24, 2023

Язык: Английский

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Post‐synthetic Rhodium (III) Complexes in Covalent Organic Frameworks for Photothermal Heterogeneous C−H Activation

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(14)

Опубликована: Янв. 20, 2024

Abstract Although photocatalytic C−H activation has been realized by using heterogeneous catalysts, most of them require high‐temperature conditions to provide the energy required for bond breakage. The catalysts with photothermal conversion properties can catalyze this reaction efficiently at room temperature, but so far, these have rarely developed. Here, we construct bifunctional Rh‐COF‐316 and ‐318 combine photosensitive covalent organic frameworks (COFs) transition‐metal catalytic moiety a post‐synthetic approach. Rh‐COF enable first time, exhibit excellent yields (up 98 %) broad scope substrates in [4+2] annulation while maintaining high stability recyclability. Significantly, work is highest yield reported far porous materials catalyzing C(sp 2 )−C(sp ) formation temperature. performances be attributed COF‐316, which enhances effect (Δ T =50.9 °C), thus accelerating exchange catalyst substrates.

Язык: Английский

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Atomically isolated Sb(CN) ₃ on sp ² -c-COFs with balanced hydrophilic and oleophilic sites for photocatalytic C-H activation

Science Advances, Год журнала: 2024, Номер 10(5)

Опубликована: Янв. 31, 2024

Activation of carbon-hydrogen (C-H) bonds is utmost importance for the synthesis vital molecules. Toward achieving efficient photocatalytic C-H activation, our investigation revealed that incorporating hydrophilic C≡N-Sb(CN)

Язык: Английский

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Applications of innovative synthetic strategies in anticancer drug Discovery: The Driving Force of new chemical reactions

Bioorganic & Medicinal Chemistry Letters, Год журнала: 2025, Номер 119, С. 130096 - 130096

Опубликована: Янв. 9, 2025

Язык: Английский

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