Catalysis with Diboron(4)/Pyridine: Application to the Broad-Scope [3 + 2] Cycloaddition of Cyclopropanes and Alkenes

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(19), С. 8870 - 8882

Опубликована: Май 9, 2022

In contrast to the extensive but non-recyclable use of tetraalkoxydiboron(4) compounds as stoichiometric reagents in diverse reactions, this article reports an atom-economical reaction using a commercial diboron(4) catalyst. The key success was designing catalytic cycle for radical [3 + 2] cycloaddition involving pyridine cocatalyst generate from catalyst and reversibly mediate transfer boronyl radicals. comparison with known transition metal-based catalysts, current features not only metal-free conditions, inexpensive stable simple operation also remarkably broadened substrate scope. particular, previously unusable cyclopropyl ketones without activating group and/or alkenes 1,2-disubstitution 1,1,2-trisubstitution patterns were successfully used first time. Consequently, challenging cyclopentane various levels substitution (65 examples, 57 new products, up six substituents at all five ring atoms) readily prepared generally high excellent yield diastereoselectivity. applied concise formal synthesis anti-obesity drug building natural product-like complex bridged or spirocyclic compounds. Mechanistic experiments computational investigation support proposed relay catalysis featuring pyridine-assisted Overall, work demonstrates approach catalysts may lead development new, green, efficient metal-like boron-catalyzed organic reactions.

Язык: Английский

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Cobalt(III)-catalyzed asymmetric ring-opening of 7-oxabenzonorbornadienes via indole C–H functionalization

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Фев. 25, 2023

Abstract Asymmetric ring-opening of 7-oxabenzonorbornadienes is achieved via Co-catalyzed indole C–H functionalization. The utilization chiral Co-catalyst consisting a binaphthyl-derived trisubstituted cyclopentadienyl ligand resulted in high yields (up to 99%) and excellent enantioselectivity (>99% ee) for the target products with tolerance diverse functional groups. Opposite diastereoselectivities are obtained or Cp*CoI 2 CO. Combined experimental computational studies suggest β -oxygen elimination being selectivity-determining step reaction. Meanwhile, reactions 7-azabenzonorbornadiene could also be executed diastereodivergent manner.

Язык: Английский

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A novel shear-stiffening supramolecular material derived from diboron structure

Science China Materials, Год журнала: 2023, Номер 66(11), С. 4489 - 4498

Опубликована: Окт. 8, 2023

Язык: Английский

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Ir-Catalyzed Ligand-Free Directed C–H Borylation of Arenes and Pharmaceuticals: Detailed Mechanistic Understanding

The Journal of Organic Chemistry, Год журнала: 2022, Номер 87(6), С. 4360 - 4375

Опубликована: Март 7, 2022

An efficient method for Ir-catalyzed ligand free ortho borylation of arenes (such as, 2-phenoxypyridines, 2-anilinopyridines, benzylamines, benzylpiperazines, benzylmorpholines, benzylpyrrolidine, benzylpiperidines, benzylazepanes, α-amino acid derivatives, aminophenylethane and other important scaffolds) pharmaceuticals has been developed. The reaction underwent via an interesting mechanistic pathway, as revealed by the detailed investigations using kinetic isotope studies DFT calculations. catalytic cycle is found to involve intermediacy Ir-boryl complex where substrate C–H activation turnover determining step, intriguingly without any appreciable primary KIE. displays a broad range scope functional group tolerance. Numerous late-stage various molecules drugs were achieved this developed strategy. borylated compounds further converted into more valuable functionalities. Moreover, utilizing benefit B–N intramolecular interaction mono compounds, operationally simple selective diborylation 2-phenoxypyridines numerous functionalized arenes. Furthermore, synthetic utility showcased with removal pyridyl directing from product achieve phenol along ipso-borylation preparation 1,2-diborylated benzene.

Язык: Английский

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Ate complexes in organic synthesis: From ate reagents to ate catalysts

Green Synthesis and Catalysis, Год журнала: 2024, Номер 5(3), С. 141 - 152

Опубликована: Май 8, 2024

The realm of application organometallic catalysis to organic synthesis has witnessed a transformative shift in recent years, owing much the evolution ate complexes from mere reagents versatile catalysts. Ate complexes, formed through coordination neutral Lewis acid with an anionic base, have emerged as pivotal intermediates that not only facilitate transformations but also serve efficient catalysts wide range chemical reactions. This review presents fascinating journey highlighting their development stoichiometric active Historically, were primarily regarded species essential for various metal-catalyzed transformations. However, constant research unveiled potential own right, reshaping landscape modern synthesis. In this minireview, we discuss role synthesis, early days reactive current stature catalytic pioneers offering glimpse into exciting future dynamic field.

Язык: Английский

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Photochemical C–H Borylation in Organic Synthesis

ACS Catalysis, Год журнала: 2025, Номер 15(3), С. 1753 - 1770

Опубликована: Янв. 16, 2025

Although C–H bond functionalization has been extensively studied since its discovery in 1955, the borylation of organic compounds by activating bonds only became popular valuable Hartwig 1995 who considered a wider application these transformations synthetic chemistry. For borylation, catalytic activation this generally low-reactivity can be performed many ways. Among approaches reported are use and stoichiometric reagents, thermal activation, photochemical suitable substrates. Iridium-, ruthenium-, rhodium-based protocols using have played crucial role toward establishment area. Photochemical though, scarcely explored despite fact that it represents comparably environmentally benign protocol light as renewable energy source. In literature survey, we highlight recent developments from initial inception up to latest advancements.

Язык: Английский

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Synthesis of naphthalene derivatives via nitrogen-to-carbon transmutation of isoquinolines

Science Advances, Год журнала: 2025, Номер 11(5)

Опубликована: Янв. 29, 2025

Heteroarene skeletal editing is gaining popularity in synthetic chemistry. Transmuting single atoms generates molecules that have distinctly varied properties, thereby fostering potent molecular exchanges can be extensively used to synthesize functional molecules. Herein, we present a convenient protocol for nitrogen-carbon single-atom transmutations isoquinolines, which inspired by the Wittig reaction and enables easy access substituted naphthalene derivatives. The uses an inexpensive commercially available phosphonium ylide as carbon source furnish wide range of naphthalenes. key success this transformation formation triene intermediate through ring opening, undergoes 6π-electrocyclization elimination processes afford product. Furthermore, strategy facile synthesis 13 C-labeled naphthalenes using CH 3 PPh I commercial C facilitates modifying directing group C─H functionalization.

Язык: Английский

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Ir-Catalyzed, Nitrogen-Directed C(sp³)–H and C(sp²)–H Borylation with a Spiro-Fluorene-Indenoindenyl Ligand

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4061 - 4068

Опубликована: Фев. 21, 2025

Язык: Английский

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Visible‐Light‐Induced, Single‐Metal‐Catalyzed, Directed C−H Functionalization: Metal‐Substrate‐Bound Complexes as Light‐Harvesting Agents

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(31)

Опубликована: Март 28, 2022

C-H functionalization represents one of the most rapidly advancing areas in organic synthesis and is regarded as key concepts to minimize ecological economic footprint synthesis. The ubiquity low reactivity bonds molecules, however, poses several challenges, often necessitates harsh reaction conditions achieve this goal, although it highly desirable reactions under mild conditions. Recently, reports uncovered a conceptually new approach towards functionalization, where single transition-metal complex can be used both photosensitizer catalyst promote bond absence an exogeneous photosensitizer. In Minireview, we will provide overview on recent achievements reactions, with emphasis photochemical modulation mechanism using such catalysts.

Язык: Английский

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Design, synthesis and visible-light-induced non-radical reactions of dual-functional Rh catalysts

Nature Synthesis, Год журнала: 2023, Номер 2(6), С. 535 - 547

Опубликована: Март 30, 2023

Язык: Английский

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