Access to Cyclohexadiene and Benzofuran Derivatives via Catalytic Arene Cyclopropanation of α-Cyanodiazocarbonyl Compounds DOI

Mei-Lin Chen,

Chi-wen Chou,

Jia‐Liang Zhu

et al.

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(27), P. 5552 - 5560

Published: Jan. 1, 2024

Catalytic arene cyclopropanation of α-cyanodiazoacetates or α-diazo-β-ketonitriles gave norcaradienes dihydrobenzofurans, which were converted to cyclohexadienes benzofurans via cyclopropanation/reductive double ring-opening DDQ oxidation.

Language: Английский

Nickel(II)-Catalyzed Asymmetric Inverse-Electron-Demand Diels–Alder Reaction of 2-Pyrones with Styrenes and Indenes DOI

Heng-Bin Yu,

Yang-Guang Chen,

Tian Yin

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 8930 - 8938

Published: May 28, 2024

With electronically unbiased styrenes and indenes as dienophiles, a highly enantioselective all-carbon-based inverse-electron-demand Diels–Alder reaction of electron-deficient 2-pyrones is reported. Using C1-symmetric imidazolidine-pyrroloimidazolone pyridine the tridentate ligand Ni(OTf)2 Lewis acid, diverse bridged bicyclic lactones were obtained in high yields (88–97% yields), diastereoselectivities (>95:5 dr), enantioselectivities (90–99% ee). Cyclic enamine 2,3-dihydrofuran also suitable dienophiles. DFT calculations supported concerted [4 + 2] cycloaddition mechanism for Ni(II) complex-catalyzed with enantioselectivity caused by steric factors.

Language: Английский

Citations

10
Recent advancements in the chemistry of Diels–Alder reaction for total synthesis of natural products: a comprehensive review (2020–2023) DOI Creative Commons
A. C. Rana, Anupam Mishra, Satish Kumar Awasthi

et al.

RSC Advances, Journal Year: 2025, Volume and Issue: 15(6), P. 4496 - 4525

Published: Jan. 1, 2025

This review covers recent advancements in Diels–Alder reaction chemistry for total synthesis of Natural Products (2020–2023) and, where relevant, discusses key structural features and biological activity bioactive natural products.

Language: Английский

Citations

2
Mechanochemical Birch Reduction with Low Reactive Alkaline Earth Metals DOI
Jagadeesh Varma Nallaparaju,

Riin Satsi,

Danylo Merzhyievskyi

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(20)

Published: March 4, 2024

Abstract Birch reduction and similar dissolved metal‐type transformations hold significant importance in the organic synthesis toolbox. Historically, field has been dominated by alkali metal reductants. In this study, we report that largely neglected, low‐reactive alkaline earth metals can become powerful affordable reductants when used a ball mill under essentially solvent‐free conditions, presence of ethylenediamine THF as liquid additives. Calcium reduce both electron‐deficient electron‐rich arenes, with yields products to those obtained lithium metal. Magnesium reveals enhanced reducing power, enabling benzoic acids while keeping aromatic moieties intact allows for chemoselective transformations. The developed mechanochemical approach uses readily available safer‐to‐handle metals, operates air ambient temperature be gram‐scale preparations. Finally, demonstrate conditions other reductive transformations, including amination, deoxygenation, dehalogenation, alkene alkyne reductions.

Language: Английский

Citations

9
Catalytic Intermolecular Asymmetric [2π + 2σ] Cycloadditions of Bicyclo[1.1.0]butanes: Practical Synthesis of Enantioenriched Highly Substituted Bicyclo[2.1.1]hexanes DOI
Yingjie Li,

Zhen Wu,

Qiang‐Shuai Gu

et al.

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

Published: Dec. 3, 2024

The high percentage of sp

Language: Английский

Citations

9
Transition metal complexes: A new era of photosensitizers for Dearomative photocycloaddition/annulation via energy and Electron transfer Photocatalysis DOI

Ram Narayan Yadav,

Ashok Srivastava, Sovan Dey

et al.

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 520, P. 216136 - 216136

Published: Aug. 14, 2024

Language: Английский

Citations

7
Enantioselective Cross-[4 + 2]-Cycloaddition/Decarboxylation of 2-Pyrones by Cooperative Catalysis of the Pd(0)/NHC Complex and Chiral Phosphoric Acid DOI
Mengmeng Xu, Pei‐Pei Xie,

Jun‐Xiong He

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(10), P. 6936 - 6946

Published: Feb. 28, 2024

Here, we describe a cooperative Pd(0)/chiral phosphoric acid catalytic system that allows us to realize the first chemo-, regio-, and enantioselective sequential cross-[4 + 2]-cycloaddition/decarboxylation reaction between 2-pyrones unactivated acyclic 1,3-dienes. The key success of this transformation is utilization an achiral N-heterocyclic carbene (NHC) as ligand newly developed chiral cocatalyst. Experimental investigations computational studies support idea Pd(0)/NHC complex acts π-Lewis base increase nucleophilicity 1,3-dienes via η2 coordination, while simultaneously increases electrophilicity by hydrogen bonding. By synergistic catalysis, 2]-cycloaddition decarboxylation proceeds efficiently, enabling preparation wide range vinyl-substituted 1,3-cyclohexadienes in good yields enantioselectivities. synthetic utility demonstrated transformations product various valuable six-membered carbocycles.

Language: Английский

Citations

6
Ni(0)‐Catalyzed Rearrangement of Vinylcyclobutanones (VCBOs) to Synthesize Six‐Membered Non‐Conjugated Enones DOI

Jiguo Ma,

Jingui Duan, Zhi‐Xiang Yu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 16, 2024

We report here the first nickel-catalyzed rearrangement of vinylcyclobutanones (VCBOs) under mild conditions to synthesize non-conjugated cyclohexenone derivatives, which so far do not have many ways be accessed. The reaction exhibits a wide substrate scope with yields up 98 %. This VCBO can also used access various n/6 (n=5-8) bicyclic products efficiently. Furthermore, mechanism this has been investigated using DFT calculations, showing that vinyl group-assisted cyclobutanone C-C cleavage is easy computed activation free energy 18.1 kcal/mol.

Language: Английский

Citations

5
Asymmetric Total Synthesis and Structural Revision of Antiangiogenic Natural Product Penduliflaworosin DOI

Xu‐Ge Si,

Quan Cai

Chinese Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 45(3), P. 959 - 959

Published: Jan. 1, 2025

Language: Английский

Citations

0
N-Heterocyclic Carbene-Catalyzed [4 + 2] Annulation of Enolizable Thioesters for the Synthesis of 2-Pyrones DOI

Jinfeng Zhang,

Chen Zhu,

Xu Cao

et al.

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

Published: April 23, 2025

An N-heterocyclic carbene (NHC)-catalyzed [4 + 2] annulation enables the direct synthesis of 2-pyrones from α-chlorothioesters and β,γ-unsaturated α-keto esters or chalcones. The method utilizes NHC-activated to generate key intermediates for 2-pyrone formation with high functional group tolerance. Moreover, were transformed into polysubstituted benzene naphthalene derivatives, showcasing their synthetic value.

Language: Английский

Citations

0
Computational Design of Ligands for the Ir-Catalyzed C5-Borylation of Indoles through Tuning Dispersion Interactions DOI
Tianyu Zheng, Jiawei Ma,

Haochi Chen

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(36), P. 25058 - 25066

Published: Aug. 29, 2024

The indole moiety is ubiquitous in natural products and pharmaceuticals. C–H borylation of the benzenoid indoles a challenging task, especially at C5 position. We have combined computational experimental studies to introduce multiple noncovalent interactions, dispersion, between substrate catalytic ligand realize C5-borylation with high reactivity selectivity. successful predictions new ligands should be suitable for design other transition-metal catalyzed reactions.

Language: Английский

Citations

2