Enantioselective Synthesis of Indole-Fused Polycycles Bearing Four Consecutive Stereocenters via Rhodium Catalysis

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 3, 2025

Indole-fused polycycles are common in natural products and bioactive molecules, yet their concise efficient synthesis remains challenging, especially for compounds with multiple stereocenters. Herein, we report the application of a chiral CpxRhIII catalyst enantioselective C–H activation/[4+2] annulation indoles bicyclic alkenes. This catalytic system exhibits high enantioselectivity broad functional group tolerance operates under benign conditions. The scope this methodology encompasses variety substrates, delivering novel polycyclic four consecutive stereocenters bridged ring good to excellent yields remarkable enantioselectivities (≤1:99 er). approach facilitates structurally diverse molecules that retain integrity while introducing chirality. More importantly, 3ab significantly inhibited proliferation CESS Kasumin-1 cells IC50 values 0.76 0.28 μM, respectively. In addition, has been demonstrated as an effective agent promoting apoptosis cells.

Language: Английский

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Accessing 7,8-Dihydroquinoline-2,5-diones via Rh-Catalyzed Olefinic C–H Activation/[4+2] Cyclization

Organic Letters, Journal Year: 2024, Volume and Issue: 26(24), P. 5136 - 5140

Published: June 7, 2024

Herein, we report a rhodium-catalyzed C–H activation/[4+2] cyclization reaction between α,β-unsaturated amides and iodonium ylides for the synthesis of novel 7,8-dihydroquinoline-2,5-diones analogues. This protocol provides series pyridones fused with saturated cycles good functional group compatibility, water air tolerance, to excellent yields under mild green conditions. Additionally, scale-up can be smoothly performed as low 0.25 mol % catalyst loading. Recycling experiments different transformation were also carried out demonstrate potential synthetic utility this protocol.

Language: Английский

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Rhodium-Catalyzed Diastereoselective C–H Activation/[4 + 2] Annulation of α,β-Unsaturated Amides with Bicyclic Alkenes

Organic Letters, Journal Year: 2024, Volume and Issue: 26(2), P. 483 - 487

Published: Jan. 10, 2024

Herein, we report a rare example of rhodium-catalyzed C–H activation/[4 + 2] annulation alkenyl amides with bicyclic alkenes under mild and green conditions. The reactivity the rhodium catalyst in this study differed from that observed cobalt-catalyzed activation/[3 between vinylic alkenes. In addition, reaction was performed EtOH at room temperature, which also displayed excellent diastereoselectivity, good functional group tolerance, air compatibility. A series novel bridged-ring skeletons were obtained to yields. Scale-up experiments carried out 1 or 0.75 mol % catalyst, affording desired skeleton

Language: Английский

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Rhodium-Catalyzed C(sp²)–H Activation and [3+3] Annulation: Accessing Pyrano[3,2-c]chromene-2,5-diones as TASK-3 Activators

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 21, 2025

Herein, an efficient Rh-catalyzed C-H activation/annulation between α,β-unsaturated amides and coumarin-derived iodonium ylides has been developed, affording novel pyrano[3,2-c]chromene-2,5-diones analogues in high yields. Most products could be easily isolated by precipitation ethanol, followed simple filtration. Additionally, this protocol demonstrated the benefits of environmentally friendly conditions, air compatibility, good functional group scale-up synthesis with low catalyst loading, a recyclable Rh catalyst. Importantly, compounds 3m 3w moderate agonist activity on TASK-3 channel, I/I0 values 1.7650 ± 0.1058 1.400 0.0589, respectively.

Language: Английский

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Design, synthesis, and mechanism study of novel natural-based isoquinolone derivatives as potential antifungal agents

Journal of Asian Natural Products Research, Journal Year: 2025, Volume and Issue: unknown, P. 1 - 14

Published: April 21, 2025

A series of isoquinolone compounds Ia-Iq containing amide moiety were rationally designed and synthesized based-on alkaloids. Their structures confirmed by 1H NMR,13C NMR HRMS. Most the title showed medium to excellent antifungal activity in vitro at 50 mg/L. Especially, EC50 Im (13.155 mg/L) against P. piricola was slightly better than chlorothalonil (14.323 mg/L). The vivo on apples comparable chlorothalonil. Preliminary mechanistic exploration illustrated that strongly damage mycelium morphology. Furthermore, molecular electrostatic potential docking analysis revealed could interact with residues SDH via hydrogen bond.

Language: Английский

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Rhodium‐Catalyzed C–H Bond Annulation for the Synthesis of 5‐ and 6‐Membered N‐Heterocyclic Building Blocks

ChemCatChem, Journal Year: 2024, Volume and Issue: unknown

Published: May 17, 2024

Abstract The sustainable preparation of N ‐heterocycles is one the most active research areas owing to their predominance as synthetics building blocks with extensive applications in organic, pharmaceutical, and material chemistry fields. Among various catalytic protocols, C−H bond functionalization concomitant C−N formation, so‐called annulation, has become routes access because it starts from low‐functionalized materials generates a limited amount waste, all respecting concept atom economy. Rhodium complexes often catalyze these reactions. This review focuses on synthesis 5‐ 6‐membered ring ‐containing heterocycles such indoles, pyrroles, indolines, (iso)quinolinones, dihydroquinolines, pyrrolidones readily available starting materials, an emphasis novel cascade synthetic methodologies via C−N/C−C well mechanisms reactions, especially oxidation steps. We hope this will help researchers looking prepare minimum steps those who want develop new based activation/functionalizations.

Language: Английский

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The synthesis of spirocyclopropane skeletons enabled by Rh(III)-catalyzed enantioselective C–H activation/[4 + 2] annulation

Chem Catalysis, Journal Year: 2023, Volume and Issue: 3(12), P. 100822 - 100822

Published: Nov. 27, 2023

Language: Английский

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Construction of Rings via Metal‐Catalyzed C−H Annulation with Unsymmetrical Internal Alkynes: Selectivity and Applications

ChemCatChem, Journal Year: 2023, Volume and Issue: 15(21)

Published: Aug. 19, 2023

Abstract Selective and concise construction of ring systems that are ubiquitous skeletons across chemistry, drugs materials, is indispensable for human life. Of note, directed C−H annulation with alkynes the expedient delivery holds great importance, featuring step‐ atom‐economy, mild conditions, broad substrate scope. However, regioselectivity issues remained when using unsymmetrical annulation. Herein, we summarized recent achievements towards solving this problem by developing directing groups, metal catalysts, versatile traceless functionality ensure overall regioselectivity, enantioselectivity, efficiency, synthetic application. We hope concept will promote further development precise functional molecules alkynes.

Language: Английский

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Rhodium-catalyzed regioselective C–H activation/Lossen rearrangement/annulation for the green synthesis of trisubstituted 2-pyridones

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(12), P. 3000 - 3009

Published: Jan. 1, 2023

A green and novel approach for the synthesis of 2-pyridone derivatives by a rhodium-catalyzed C–H activation/Lossen rearrangement acrylamides propargyl alcohols is reported.

Language: Английский

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Direct C–H difluoroallylation of α,β-unsaturated amides and aryl amides by rhodium catalysis

Chemical Communications, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

The first example of Rh-catalyzed C(sp 2 )–H difluoroallylation α,β-unsaturated amides with 3-bromo-3,3-difluoropropene has been developed under mild conditions.

Language: Английский

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