[reaction: see text] A novel oxidative photodehydrocyclization of indolinylphenylethenes to a polycyclic heteroaromatic cation with good yields was described. Starting from the trans derivative, the phototransformation is a multistep process. The process includes two photochemical reactions and a trans-cis isomerization reaction, followed by an 1-aza-1,3,5-hexatrienic electrocyclic reaction involving the formation of a C-N bond. The cyclized product gives the stable heteroaromatic cations from hydride elimination with oxygen from air or iodine.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/ol034848e | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Transformative reactions in nitroarene chemistry: C-N bond cleavage, skeletal editing, and N-O bond utilization.
Org Biomol Chem
January 2025
Department of Applied Chemistry, Waseda University, 513 Wasedatsurumakicho, Shinjuku, Tokyo 162-0041, Japan.
Nitroarenes are highly versatile building blocks in organic synthesis, playing a pivotal role in various reactions. Common transformations involving nitroarenes include nucleophilic aromatic substitution (SAr) reactions, where the nitro group functions both as a potent electron-withdrawing group that activates the aromatic ring and as a leaving group facilitating the substitution. Additionally, the direct transformation of nitro groups, such as reduction-driven syntheses of amines and carboxylic acids, as well as -substitution SAr reactions, have been extensively explored.
View Article and Find Full Text PDFHarnessing Adsorbate-adsorbate Interaction to Activate C-N Bond for Exceptional Photoelectrochemical Urea Oxidation.
Angew Chem Int Ed Engl
January 2025
Institute of Chemistry CAS: Institute of Chemistry Chinese Academy of Sciences, Beijing National Laboratory for Molecular Sciences, Zhongguancun North First St, 100190, Beijing, CHINA.
The photoelectrochemical (PEC) urea oxidation reaction (UOR) presents a promising half-reaction for green hydrogen production, but the stable resonance structure of the urea molecule results in sluggish kinetics for breaking the C-N bond. Herein, we realize the record PEC UOR performance on a NiO-modified n-Si photoanode (NiO@Ni/n-Si) by harnessing the adsorbate-adsorbate interaction. We quantificationally unveil a dependence of the UOR activation barrier on the coverage of photogenerated surface high-valent Ni-oxo species (NiIV=O) by employing operando PEC spectroscopic measurements and theoretical simulations.
View Article and Find Full Text PDFExploring a metal/base-free porphyrin involving a carboxyl-functionalized pyridine moiety for photocatalytic -arylation of benzamide validated using RSM.
Org Biomol Chem
January 2025
Department of Chemistry, School of Advanced Sciences, Vellore Institute of Technology, Vellore, Tamil Nadu-632014, India.
A porphyrin comprising a carboxyl-functionalized pyridine moiety was synthesized and characterized using H NMR, C NMR, FT-IR, powder-XRD, BET, ICP-MS, SEM and EDAX. The proton level (H = 1.19) and energy band gap (1.
View Article and Find Full Text PDFPhoto-Driven Direct Construction of Imidazolidines from Anilines and Paraformaldehyde and Its Application in Polyoxymethylene Plastics Usage.
Chem Asian J
January 2025
Leibniz-Institut fur Katalyse eV, organmetallic and catalyst, Albert-Einstein-Str. 29a, 18059, Rostock, GERMANY.
Imidazolines play pivotal roles in numerous fields. However, the direct construction of imidazolines from primary amines involves precise C-C and C-N bond formations, rendering this area still underdeveloped to this day. Herein, a photo-driven metal-free catalytic system has been successfully applied to a novel coupling-cyclization reaction between arylamines and formaldehyde, enabling the direct synthesis of various 1,3-diarylimidazolines from primary amines.
View Article and Find Full Text PDFAlkylazolation of Alkenes via Photocatalytic Radical Polar Crossover.
Org Lett
January 2025
Department of Chemistry, University of Hawai'i at Ma̅noa, Honolulu, Hawaii 96822, United States.
We present a photocatalytic method for alkylamination of alkenes, enabling efficient C-C and C-N bond formation to construct aza-heterocycles valuable in drug discovery. Using a radical-polar crossover pathway, electron-deficient alkenes are reduced to electrophilic radicals, which react with electron-rich alkenes to form nucleophilic radicals. Oxidation of these intermediates yields carbocations, which are trapped by aza-heteroarenes to afford alkylaminated products.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!