Double strain-release enables formal C–O/C–F and C–N/C–F ring-opening metathesis

Chemical Science, Год журнала: 2024, Номер 15(34), С. 13800 - 13806

Опубликована: Янв. 1, 2024

Metathesis reactions have been established as a powerful tool in organic synthesis. While great advances were achieved double-bond metathesis, like olefin metathesis and carbonyl single-bond has received less attention the past decade. Herein, we describe first C(sp

Язык: Английский

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Preserving precise choreography of bonds in Z-stereoretentive olefin metathesis by using quinoxaline-2,3-dithiolate ligand

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

Опубликована: Окт. 17, 2024

The Z-alkene geometry is prevalent in various chemical compounds, including numerous building blocks, fine chemicals, and natural products. Unfortunately, established Mo, W, Ru Z-selective catalysts lose their selectivity at high temperatures required for industrial processes like reactive distillation, which limits synthetic applications. To address this issue, we develop a catalyst capable of providing Z-alkenes with under harsh conditions. Our research reveals dithiolate ligand that, stabilised by resonance, delivers up to 150 °C concentrated mixtures. This distinguishes the dithioquinoxaline complex from existing catalysts. Notably, trait does not compromise new catalyst's usability classical conditions, matching activity known stereoretentive Density Functional Theory calculations were employed understand reaction mechanism selectivity, investigate poisoning that may undergo how it competes catalytic activity. Furthermore, quinoxaline-based enables valorisation bio-sourced alkene feedstocks production agricultural sex pheromones pest control.

Язык: Английский

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Molybdenum Catalyzed Acceptorless Dehydrogenation of Alcohols for the Synthesis of Quinolines

ChemCatChem, Год журнала: 2024, Номер 16(15)

Опубликована: Фев. 23, 2024

Abstract The first molybdenum triazolylidene complexes catalyzing the atom‐economical synthesis of quinolines through acceptorless dehydrogenative coupling alcohols is reported. A new family Mo(0) bearing chelating bis‐1,2,3‐triazolylidene, pyridyl‐1,2,3‐triazolylidene, and bis‐triazole ligands have been prepared applied as catalysts for quinolines. Interestingly, Mo bis‐1,2,3‐triazolylidene with alkyl groups (Et, n ‐Bu) displayed superior catalytic activities than those containing aryl substituents on rings. Control experiments corroborated that reaction involves dehydrogenation pathway.

Язык: Английский

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(1R)-2,3,4,6-Tetra-O-benzyl-1-C-allyl-1-deoxy-1-C-(2-thiazolyl)-D-galactopyranose

Molbank, Год журнала: 2025, Номер 2025(1), С. M1949 - M1949

Опубликована: Янв. 8, 2025

We have previously reported that thiazolylketol acetates, synthesized by the addition of 2-lithiothiazole to sugar lactones followed acetylation, are efficient glycosyl donors affording O-, N-, P-, and C-glycosides. After first example C-glycosidation recently described us, we report here on unexpected outcome reaction a acetate with allyltrimethylsilane in presence trimethylsilyl triflate. The obtained intermediate, an intramolecular N-thiazolium salt, could be stereoselectively converted into desired allyl C-thiazolylketoside.

Язык: Английский

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Three-component synthesis of β-sulfonyl enamines and dienamines enabled by silver(i) acetate

RSC Advances, Год журнала: 2025, Номер 15(5), С. 3602 - 3606

Опубликована: Янв. 1, 2025

The three-component synthesis of β-sulfonyl enamines and δ-sulfonyl dienamines is achieved by silver acetate-mediated condensation secondary tertiary amines with sodium sulfinates.

Язык: Английский

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Catalytic prenyl conjugate additions for synthesis of enantiomerically enriched PPAPs

Science, Год журнала: 2024, Номер 386(6718), С. 167 - 175

Опубликована: Окт. 10, 2024

Polycyclic polyprenylated acylphloroglucinols (PPAPs) are a class of >400 natural products with broad spectrum bioactivity, ranging from antidepressant and antimicrobial to anti-obesity anticancer activity. Here, we present scalable, regio-, site-, enantioselective catalytic method for synthesis cyclic β-prenyl ketones, compounds that can be used efficient syntheses many PPAPs in high enantiomeric purity. The transformation is prenyl conjugate addition β-ketoesters promoted by readily accessible chiral copper catalyst involving an easy-to-prepare isolable organoborate reagent. Reactions reach completion just few minutes at room temperature. importance this advance highlighted the preparation intermediates previously generate racemic PPAPs. We also nemorosonol (14 steps, 20% yield) its one-step conversion another PPAP, garcibracteatone (52% yield).

Язык: Английский

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Preserving Precise Choreography of Bonds in Stereoretentive Olefin Metathesis: New Type of Ligand Allows High Z-Selectivity Even at Elevated Temperature

Опубликована: Май 17, 2024

The Z-alkene geometry is prevalent in various chemical compounds, including numerous building blocks, fine chemicals, and natural products. Unfortunately, established Mo, W, Ru Z‑selective catalysts lose their selectivity at high temperatures required for industrial processes like reactive distillation, which limits synthetic applications. To address this issue, we developed a catalyst capable of providing Z-alkenes with under harsh conditions. Our research revealed novel dithiolate ligand that, stabilised by resonance, delivers up to 150 °C concentrated mixtures. This distinguishes the dithioquinoxaline complex from existing Z-selective catalysts. Notably, unique trait does not compromise new catalyst’s usability classical conditions, matching activity known stereoretentive Density Functional Theory (DFT) calculations were employed understand reaction mechanism selectivity, investigate poisoning that may undergo how it competes catalytic activity. Furthermore, quinoxaline-based enables valorisation bio-sourced alkene feedstocks production agricultural sex pheromones pest control.

Язык: Английский

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Cobalt-Catalyzed Chemo- and Stereoselective Transfer Semihydrogenation of 1,3-Dienes with Water as a Hydrogen Source

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(33), С. 23476 - 23486

Опубликована: Авг. 7, 2024

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Synthesis of Z-gem-Cl,CF₃-Substituted Alkenes by Stereoselective Cross-Metathesis and the Role of Disubstituted Mo Alkylidenes

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(32), С. 22485 - 22497

Опубликована: Июль 30, 2024

Stereochemically defined organofluorine compounds are central to drug discovery and development. Here, we present a catalytic cross-metathesis method for the synthesis of

Язык: Английский

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Transition-metal-free isofunctional reaction of α,β-unsaturated ketones/nitriles

Science China Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Сен. 29, 2024

Язык: Английский

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