Metal-catalysed C–H bond activation and borylation

Chemical Society Reviews, Год журнала: 2022, Номер 51(12), С. 5042 - 5100

Опубликована: Янв. 1, 2022

Transition metal-catalysed direct borylation of hydrocarbons via C–H bond activation has received a remarkable level attention as popular reaction in the synthesis organoboron compounds owing to their synthetic versatility.

Язык: Английский

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Transition-Metal-Catalyzed Silylation and Borylation of C–H Bonds for the Synthesis and Functionalization of Complex Molecules

Chemical Reviews, Год журнала: 2023, Номер 123(19), С. 11619 - 11663

Опубликована: Сен. 26, 2023

The functionalization of C–H bonds in organic molecules containing functional groups has been one the holy grails catalysis. One synthetically important approach to diverse is catalytic silylation or borylation bonds, which enables a broad array downstream transformations afford structures. Advances both undirected and directed methods for transition-metal-catalyzed have led their rapid adoption early-, mid-, late-stage synthesis complex molecules. In this Review, we review application bioactive molecules, materials, ligands. Overall, aim provide picture state art as applied modification architectures that will spur further development these reactions.

Язык: Английский

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Transition metal–catalyzed remote C─H borylation: An emerging synthetic tool

Science Advances, Год журнала: 2023, Номер 9(16)

Опубликована: Апрель 21, 2023

Transition metal–catalyzed C─H bond activation and borylation is a powerful synthetic method that offers versatile transformation from organoboron compounds to virtually all other functional groups. Compared the ortho-borylation, remote remains more challenging owing inaccessibility of these bonds. Enforcing metal catalyst toward bonds needs well-judged design through proper ligand development. This review article aims summarize recent discoveries for by employment new catalyst/ligand with help steric ligand, noncovalent interactions. It has been found now takes part in total synthesis natural products shorter route. Whereas, Ir-catalyzed predominant, cobalt also started affect this field sustainable cost-effective

Язык: Английский

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Ruthenium‐Catalyzed Stereo‐ and Site‐Selective ortho‐ and meta‐C−H Glycosylation and Mechanistic Studies

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(32)

Опубликована: Июнь 8, 2022

Abstract C‐aryl glycosides are popular basic skeletons in biochemistry and pharmaceutical chemistry. Herein, ruthenium‐catalyzed highly stereo‐ site‐selective ortho ‐ meta ‐C Ar −H glycosylation is described. A series of pyranosides furanosides were synthesized by this method. The strategy showed good substrate scope, various N ‐heterocyclic directing groups compatible with the reaction system. mechanistic study suggested that key pathway might involve oxidative addition/reduction elimination, whereas aryl ‐C−H was mediated σ ‐activation. Density functional theory calculations also high stereoselectivity due to steric hindrance.

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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N-heterocyclic carbene- and organic photoredox-catalysed meta-selective acylation of electron-rich arenes

Nature Synthesis, Год журнала: 2023, Номер 2(11), С. 1037 - 1045

Опубликована: Авг. 3, 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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Kinetic and thermodynamic control of C(sp ² )–H activation enables site-selective borylation

Science, Год журнала: 2023, Номер 382(6675), С. 1165 - 1170

Опубликована: Дек. 7, 2023

Catalysts that distinguish between electronically distinct carbon-hydrogen (C–H) bonds without relying on steric effects or directing groups are challenging to design. In this work, cobalt precatalysts supported by N -alkyl-imidazole–substituted pyridine dicarbene (ACNC) pincer ligands described enable undirected, remote borylation of fluoroaromatics and expansion scope include electron-rich arenes, pyridines, tri- difluoromethoxylated thereby addressing one the major limitations first-row transition metal C–H functionalization catalysts. Mechanistic studies established a kinetic preference for bond activation at meta -position despite cobalt-aryl complexes resulting from ortho being thermodynamically preferred. Switchable site selectivity in as function boron reagent was preliminarily demonstrated using single precatalyst.

Язык: Английский

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Silylarylation of Alkenes via meta-Selective C–H Activation of Arenes under Ruthenium/Iron Cooperative Catalysis: Mechanistic Insights from Combined Experimental and Computational Studies

ACS Catalysis, Год журнала: 2024, Номер 14(7), С. 4510 - 4522

Опубликована: Март 12, 2024

Organosilicons are privileged skeletons in the domains of pharmaceutical chemistry, organic synthesis, and materials science. Hence, investigating catalytic techniques for synthesis organosilicon compounds has received a great deal emphasis. Carbosilylation alkenes is an efficient technique to introduce diverse molecular architectures containing silicon into chemical space. However, organohalides pseudohalides prerequisites most existing carbosilylation protocols. On other hand, utilization C–H activation been sowing seeds successful development intricate scaffolds. In this regard, synthetic accessibility complexed derivatives by through meta-C–H approach remained intangible. Herein, we present three-component strategy arylsilylation olefins with (het)arenes silanes integrating iron-catalyzed silyl radical generation, coupled intrinsic reactivity alkene, ruthenium-catalyzed functionalization (het)arene, leading targeted cross-coupled carbosilylated product. addition, theoretical investigations state-of-the-art dispersion corrected density functional theory at B3PW91-D3/Def2TZVP/CPCM(PhCF3) shed intriguing insights on selectivity probable mechanistic pathway underexplored cooperative 3d/4d transition metal catalysis, such as formation its addition alkene catalyzed iron, followed meta-selective ruthenium bound arene, furnishing C4 substituted (het)arene functionalized compounds.

Язык: Английский

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Noncovalent interaction with a spirobipyridine ligand enables efficient iridium-catalyzed C–H activation

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Апрель 17, 2024

Abstract Exploitation of noncovalent interactions for recognition an organic substrate has received much attention the design metal catalysts in synthesis. The CH–π interaction is especially interest molecular because both C–H bonds and π electrons are fundamental properties molecules. However, their weak nature, these have been less utilized control reactions. We show here that can be used to kinetically accelerate catalytic activation arenes by directly recognizing π-electrons arene substrates with a spirobipyridine ligand. Computation ligand kinetic isotope effect study provide evidence between backbone substrate. rational exploitation will open new avenues catalysis.

Язык: Английский

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