Type of Tetrahydronaphthalene-Fused 1,5-Dipoles and Their Application in Polycyclic Compounds Synthesis DOI
Zhengyu Han,

Xue Yu,

Hongling Xie

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(15), P. 10551 - 10556

Published: July 17, 2024

Palladium-catalyzed dipolar cycloaddition reactions represent an efficient strategy for the construction of cyclic compounds, with development novel precursors being a key focus. In this study, new type precursor was synthesized through assembly vinylethylene carbonate unit and tetrahydronaphthalene skeleton. This can undergo [3 + 2], [5 4], 2] reactions, leading to tetrahydronaphthalene-fused oxazolidin-2-ones, 1,5-oxazonines, tetrahydrooxepines. general, all these exhibited good reaction efficiency functional group tolerance.

Language: Английский

Dynamic Kinetic Activation of Aziridines Enables Radical-Polar Crossover (4 + 3) Cycloaddition with 1,3-Dienes DOI
Lei Wang, Panpan Zhou, Dong Xie

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 10, 2025

The cycloaddition of aziridines with unsaturated compounds is a valuable method for synthesizing nitrogen heterocycles. However, this process predominantly substrate-controlled, posing significant challenges in regulating the regioselectivity C–N bond cleavage. In study, we report nickel-catalyzed dynamic kinetic activation strategy that enables catalyst-controlled aziridines. Various types aziridines, including 2-phenyl, 2-carbonyl, 2-alkyl, and disubstituted consistently cleave their more sterically hindered bonds to generate 1,3-radical anion intermediates. These intermediates participate highly regioselective 1,4-Heck/allylic substitution cascade aromatic branched 1,3-dienes, resulting radical-polar crossover (4 + 3) produces seven-membered azepine products. This approach not only complements traditional dipolar cycloaddition, which typically act as zwitterionic 1,3-dipoles, but also introduces an unusual mode 1,3-dienes. Experimental investigations density functional theory (DFT) calculations provide insight into reaction mechanism.

Language: Английский

Citations

1

Lewis Base Controlled (4 + 3) and (4 + 2) Annulations of MBH Carbonates with Benzofuran‐derived Azadienes: Access to Highly Substituted Benzofuro[3,2‐b]azepines and Spirotetrahydroquinolines DOI
Kai‐Kai Wang,

Ya‐Fei Li,

Lanxin Li

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(21), P. 4521 - 4527

Published: Aug. 7, 2024

Abstract Catalyst‐controlled switchable (4+3) and (4+2) annulation reactions of Morita–Baylis–Hillman carbonates with benzofuran‐derived azadienes have been established. Employing PCy 3 as the catalyst, reaction could provide a variety synthetically useful benzofuro[3,2‐ b ]azepines in good yields (80–92%) excellent chemo‐ regioselectivities via cycloaddition reactions. Whereas changing catalyst from to DMAP, were switched construct highly substituted spirotetrahydroquinoline scaffolds three sequential stereocenters containing all‐carbon spiro‐quaternary efficiency diastereoselectivities (92–96% all cases>25:1 dr ) annulations. In addition, synthetic utility this method was further showcased by gram‐scale transformations product.

Language: Английский

Citations

4

Pd-Catalyzed Migratory 1,1-Cycloannulation Reaction of Alkenes DOI

Jinping Wang,

Tao Liu, Yichen Wu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 18, 2024

Here, we report a novel strategy for the preparation of diverse heterocycles via Pd-catalyzed migratory 1,1-cycloannulation reaction (MCAR) alkenes. Starting from readily available alkenyl amines and alcohols, this approach allows formation wide range five- to seven-membered azaheterocycles oxaheterocycles with high efficiency good functional group tolerance. The key realization is use 4-iodophenol or 2-iodophenol derivatives where phenolic hydroxyl plays critical role in controlling direction migration ring-size through quinone methide intermediate.

Language: Английский

Citations

3

Three-Component 1,3-Difunctionalization of Carbonyl Ylides with Water and Azadienes for the Synthesis of Dihydroisobenzofurans DOI
Haiqing Wang,

Yunzhe Wang,

Jie Ren

et al.

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

Published: March 27, 2025

Multicomponent reactions are an efficient and widely employed synthetic strategy, known for their capability to rapidly effectively construct complex molecular architectures from multiple starting materials. This work presents a chemo- diastereoselective three-component reaction the 1,3-difunctionalization of transient carbonyl ylides with H2O azadienes, facilitated by synergistic catalysis Rh2(OAc)4 phosphoric acid. strategy provides protocol synthesis highly functionalized dihydroisobenzofurans in high yields (up 94%) good diastereoselectivities 91:9 dr). Additionally, subsequent transformations nucleophiles enable structurally diverse compounds enhanced (dr >95:5).

Language: Английский

Citations

0

Gold(I)-Catalyzed Asymmetric Heterocyclization/(5 + 3) Cycloaddition of Yne-enones with Imidazolidines: Access to Cycloocta[c]furan Frameworks DOI
Yuncheng Liu,

X.-Y. Liu,

Song Gao

et al.

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

Published: May 12, 2025

Herein, we report a gold(I)-catalyzed heterocyclization/(5 + 3) cycloaddition cascade of yne-enones with imidazolidines, providing modular, atom-economical and efficient strategy for the synthesis cycloocta[c]furans in moderate to excellent yields. This method features readily available substrates, simple operation, mild reaction conditions, broad substrate scope. More importantly, asymmetric version is also achieved by employing (R)-C2-TunePhos ligand (L7), leading optically active up 98:2 er.

Language: Английский

Citations

0

Decarboxylative Cyclization of Ethynyl Benzoxazinanones with Imidazolidines to Access 2,3-Indole-Fused 1,4-Diazocines DOI

Zhangru Cheng,

Jiadong Chen, Yulu Zhang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(23), P. 4863 - 4867

Published: June 4, 2024

2,3-Indole-fused 1,4-diazocines represent a new family of indole alkaloid compounds and are difficult to access by the reported protocols. Herein, we report copper-catalyzed decarboxylative cyclization cyclic propargylic carbamates with imidazolidines via sequential C-N/C-N/C-C bond formation deliver series 2,3-indole-fused 1,4-diazocines, broad substrate scope mild conditions.

Language: Английский

Citations

2

Catalytic [4+2]- and [4+4]-cycloaddition using furan-fused cyclobutanone as a privileged C4 synthon DOI Creative Commons

Kemiao Hong,

Mengting Liu,

Lixin Qian

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: June 26, 2024

Abstract Cycloaddition reactions play a pivotal role in synthetic chemistry for the direct assembly of cyclic architectures. However, hurdles remain extending C4 synthon to construct diverse heterocycles via programmable [4+n]-cycloaddition. Here we report an atom-economic and modular intermolecular cycloaddition using furan-fused cyclobutanones (FCBs) as versatile synthon. In contrast well-documented benzocyclobutenones, this is complementary version FCB reagent. It involves C-C bond activation sequence, including Rh-catalyzed enantioselective [4 + 2]-cycloaddition with imines Au-catalyzed diastereoselective 4]-cycloaddition anthranils. The obtained lactams, which are motifs that present many natural products, bioactive molecules, materials, inaccessible or difficult prepare by other methods. Preliminary antitumor activity study indicates 6e 6 f exhibit high anticancer potency against colon cancer cells (HCT-116, IC 50 = 0.50 ± 0.05 μM) esophageal squamous cell carcinoma (KYSE-520, 0.89 0.13 μM), respectively.

Language: Английский

Citations

2

Expedient synthesis of 8-membered azasultams: A combined synthetic, DFT, and in vitro study DOI Creative Commons
Heorhii V. Posternak,

Olena D. Semoshkina,

Vasyl Y. Hys

et al.

Tetrahedron Chem, Journal Year: 2024, Volume and Issue: 11, P. 100085 - 100085

Published: July 17, 2024

Language: Английский

Citations

2

Highly Enantioselective Construction of Chiral Eight-Membered Cyclic Ethers through Tandem Cyclization of Ynones and Dicarbonyl Compounds DOI
Yuzhen Chen,

Peishan Gu,

Jialiang Qin

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(22), P. 16736 - 16749

Published: Oct. 30, 2024

The enantioselective synthesis of eight-membered cyclic ether has always been a challenge in organic synthesis. Herein, we reported highly tandem cyclization reaction alkyne ketone and dioxypyridines mediated by chiral bifunctional catalysts. This generates two adjacent stereocenters using an atomeconomic manner, providing simple effective method for the one-step ethers.

Language: Английский

Citations

2

Kinetic resolution of 1-(1-alkynyl)cyclopropyl ketones via gold-catalyzed divergent (4 + 4) cycloadditions: stereoselective access to furan fused eight-membered heterocycles DOI Creative Commons

Xunhua Wang,

Ruifeng Lv,

Xiaoxun Li

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(24), P. 9361 - 9368

Published: Jan. 1, 2024

The stereoselective construction of furan/pyrrole-fused eight-membered heterocycles via chiral gold-catalyzed (4 + 4) cycloadditions was realized.

Language: Английский

Citations

1