Multiple-fold C–F bond functionalization for the synthesis of (hetero)cyclic compounds: fluorine as a detachable chemical handle

Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(7), С. 2013 - 2055

Опубликована: Янв. 1, 2022

We highlighted the recent advances in field of multiple-fold C–F bond functionalization for synthesis (hetero)cyclic compounds.

Язык: Английский

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Additive-Controlled Divergent Synthesis of Tetrasubstituted 1,3-Enynes and Alkynylated 3H-Pyrrolo[1,2-a]indol-3-ones via Rhodium Catalysis

Organic Letters, Год журнала: 2021, Номер 23(3), С. 727 - 733

Опубликована: Янв. 8, 2021

Herein, we report the additive-controlled divergent synthesis of tetrasubstituted 1,3-enynes and alkynylated 3H-pyrrolo[1,2-a]indol-3-ones through rhodium-catalyzed C-H alkenylation/DG migration [3+2] annulation, respectively. This protocol features rare directing group in 1,3-diyne-involved activation, excellent regio- stereoselectivity, monofunctionalization over difunctionalization, broad substrate scope, moderate to high yields, good functional compatibility, mild redox-neutral conditions.

Язык: Английский

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Selective Synthesis of 3‐(α‐Fluorovinyl)indoles and 3‐Acylindoles via the Cascade Reactions of 1‐Phenylpyrazolidinones with α,α‐Difluoromethylene Alkynes

Advanced Synthesis & Catalysis, Год журнала: 2021, Номер 363(14), С. 3600 - 3606

Опубликована: Июнь 10, 2021

Abstract Presented herein is a selective synthesis of 3‐(α‐fluorovinyl)indoles and 3‐acylindoles via the coupling 1‐phenylpyrazolidinones with α,α‐difluoromethylene alkynes. Mechanistically, formation resulted from cascade process including Rh(III)‐catalyzed ortho ‐C−H bond cleavage, regioselective triple insertion, pyrazolidinone ring‐opening, indole ring‐formation HF elimination. Interestingly, when this reaction was carried out in CH 3 OH/H 2 O instead CN, situ formed readily undergo hydration to afford 3‐acylindole derivatives. This protocol features controllable selectivity, simultaneous both heterocyclic scaffold monofluoroalkenyl moiety, atom‐economy, substrate diversity, good functional group tolerance redox‐neutral conditions. Anticancer screening selected products against two human cancer cell lines demonstrated their potential as lead compounds for drug development. magnified image

Язык: Английский

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An overview of the reactions involving azomethine imines over half a decade

New Journal of Chemistry, Год журнала: 2021, Номер 45(20), С. 8847 - 8873

Опубликована: Янв. 1, 2021

Azomethine imines constitute a versatile class of 1,3-dipoles which was used extensively for biologically relevant N-heterocycle synthesis – five-year recap.

Язык: Английский

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Gem-Difluorocyclopropenes as Versatile β-Monofluorinated Three-sp² Carbon Sources for Cp*Rh(III)-Catalyzed [4 + 3] Annulation: Experimental Development and Mechanistic Insight

ACS Catalysis, Год журнала: 2021, Номер 11(23), С. 14694 - 14701

Опубликована: Ноя. 23, 2021

Cp*Rh(III)-catalyzed [4 + 3] annulation of N-methoxy amides for the direct assembly seven-numbered 2H-azepin-2-one frameworks has been realized with gem-difluorocyclopropenes acting as innovative β-monofluorinated three sp2 carbon sources. Either annular arylamides or linear acrylamides embedment various functional groups, including DNA-tagged substrates, were found to be compatible established reaction mode. A redox-neutral Rh(III)–Rh(V)–Rh(III) catalytic cycle, specifically via HOAc-assisted tandem site-/regioselective oxidative addition/reductive elimination/C–F bond cleavage-enabled ring-scission involving unprecedented olefinic C(sp2)–C(sp2) cleavage, deduced based on experimental and computational mechanistic studies. Taken together, our findings not only identified potent efficient coupling partners C–H activation development but also provided a sound basis organic integration transition-metal-catalyzed functionalization cyclopropene fluorine chemistries.

Язык: Английский

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Transition Metal-Controlled Divergent Annulations of Azomethine Imines with Iodonium Ylides via C-Centered [1,2]-Rearrangement

Organic Letters, Год журнала: 2023, Номер 25(15), С. 2582 - 2587

Опубликована: Апрель 10, 2023

Transition metal-controlled divergent annulation reactions of azomethine imines with iodonium ylides via C-centered [1,2]-rearrangement have been developed. The imino group, as a switchable and transient directing group (DG), underwent intramolecular nucleophilic addition in situ generated bicyclic diaziridine, which facilitated the subsequent annulations presence different metal complexes catalysts. benzo[c]chromen-1-one pyrano[de]isochromene scaffolds could be independently constructed Rh(III) Ru(II), respectively. It was worth noting that employed first DG through rearrangement progress.

Язык: Английский

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A divergent construction of fused and bridged carbo-/heterocyclic scaffoldsviacascade reactions of aryl azomethine imines with vinyl cyclic carbonates

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(4), С. 1015 - 1021

Опубликована: Янв. 1, 2023

Presented herein is a divergent synthesis of indene-fused pyrazoles and bridged benzodiazepines tethered with hydroxymethyl group through the cascade reactions aryl azomethine imines vinyl cyclic carbonates.

Язык: Английский

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Experimental and computational journey on transition-metal-catalyzed C H functionalization with fluorinated π-systems

Coordination Chemistry Reviews, Год журнала: 2024, Номер 522, С. 216244 - 216244

Опубликована: Сен. 24, 2024

Язык: Английский

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Synthesis of tetracyclic indenopyrazolopyrazolones through cascade reactions of aryl azomethine imines with propargyl alcohols

Organic Chemistry Frontiers, Год журнала: 2021, Номер 8(14), С. 3734 - 3739

Опубликована: Янв. 1, 2021

Presented herein is a novel and efficient synthesis of tetracyclic indenopyrazolopyrazolone derivatives from aryl azomethine imines propargyl alcohols through an initial inert C(sp²)–H bond alkenylation followed by the cascade formation two five-membered rings.

Язык: Английский

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Lossen Rearrangement vs C–N Reductive Elimination Enabled by Rh(III)-Catalyzed C–H Activation/Selective Lactone Ring-Opening: Chemodivergent Synthesis of Quinolinones and Dihydroisoquinolinones

Organic Letters, Год журнала: 2020, Номер 22(24), С. 9677 - 9682

Опубликована: Дек. 4, 2020

An unprecedented Rh(III)-catalyzed cascade C–H activation/Lossen rearrangement of aromatic amides with methyleneoxetanones has been realized along a tunable C–N bond reductive elimination/trans esterification, giving divergent access to quinolinones and dihydroisoquinolinones via selective ring-opening the four-membered lactone unit. Combined computational experimental mechanistic studies defined solvent-involved distinguished reaction paths, origin observed chemodivergence, as well role substituent attached at oxidizing directing group in tuning outcomes.

Язык: Английский

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