A new atom-economical synthesis of β-alkenyl-substituted BODIPYs via indium(III)-catalyzed intermolecular alkyne hydroarylation with -substituted BODIPYs is described. While catalysis with InI allows the double β-functionalization of BODIPY, resulting in regioselectively branched β,β'-disubstituted alkenyl BODIPYs, catalytic InCl enables the formation of linear β-substituted alkenyl BODIPYs. Subsequent In(III)-catalyzed intermolecular alkyne hydroarylation allows the synthesis of unsymmetrical - BODIPY derivatives. Therefore, indium catalysis offers complementary regioselectivity in good chemical yields and functional group tolerance. The resulting BODIPY dyes displayed bathochromically shifted absorption and emission according to the electron-nature of the substituents in the alkenyl moiety with high molar extinction coefficients (ε up to 88,200 M cm) and quantum yields (0.14-0.96).
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC11002825 | PMC |
| http://dx.doi.org/10.1021/acs.joc.3c02951 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Copper-Catalyzed Intermolecular [2 + 2 + 2] Annulation of Diynes with Alkynes: Construction of Carbazoles.
Org Lett
January 2025
Key Laboratory of Chemical Biology of Fujian Province and State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
Transition-metal-catalyzed [2 + 2 + 2] annulation of alkynes is an efficient pathway for the synthesis of aromatic compounds. However, most of the established methods require noble metal catalysts. Herein, we report a copper-catalyzed intermolecular [2 + 2 + 2] annulation of diynes with alkynes through vinyl cation intermediates, enabling the atom-economical preparation of biologically important carbazole skeletons.
View Article and Find Full Text PDFIntermediate Control: Unlocking Hitherto Unknown Reactivity and Selectivity in N-Conjugated Allenes and Alkynes.
Acc Chem Res
January 2025
Department of Chemistry and Chemistry Institution for Functional Materials, Pusan National University, Busan 46241, Republic of Korea.
ConspectusControlling selectivity through manipulation of reaction intermediates remains one of the most enduring challenges in organic chemistry, providing novel solutions for selective C-C π-bond functionalization. This approach, guided by activation principles, provides an effective method for selective functional group installation, enabling direct synthesis of organic molecules that are inaccessible through conventional pathways. In particular, the selective functionalization of N-conjugated allenes and alkynes has emerged as a promising research focus, driven by advances in controlling reactive intermediates and activation strategies.
View Article and Find Full Text PDFAsymmetrically PEGylated and amphipathic heptamethine indocyanine dyes potentiate radiotherapy of renal cell carcinoma via mitochondrial targeting.
J Nanobiotechnology
December 2024
Institute of Combined Injury, National Key Laboratory of Trauma and Chemical Poisoning, Army Key Laboratory of Nanomedicine, Department of Military Preventive Medicine, Army Medical University (Third Military Medical University), Chongqing, 400038, China.
Enhancing the sensitivity of radiotherapy (RT) towards renal cell carcinoma (RCC) remains a challenge because RCC is a radioresistant tumor. In this work, we design and report asymmetrically Polyethylene Glycol (PEG)ylated and amphipathic heptamethine indocyanine dyes for efficient radiosensitization of RCC treatment. They were synthesized by modifying different lengths of PEG chains as hydrophilic moieties on one N-alkyl chain of a mitochondria-targeting heptamethine indocyanine dye (IR-808), and a radiosensitizer 2-nitroimidazole (NM) as a hydrophobic moiety on another N-alkyl chain.
View Article and Find Full Text PDFProgrammable Synthesis of Cationic Azaperylenes via Rh(III)-Catalyzed Multiple C-H/N-H Bonds Activation and Annulation.
Org Lett
December 2024
Guangxi Key Laboratory of Electrochemical and Magneto-Chemical Functional Materials, College of Chemistry and Bioengineering, Guilin University of Technology, Guilin 541004, China.
Rh(III)-catalyzed dual N-H and triple C-H activation/(4 + 2) annulation of 2-aryl-2,3-dihydro-1-perimidines and alkynes has been disclosed to construct 4,5,14,15-tetrasubstituted cationic azaperylenes with high yields (up to 95%) and broad scope. Tandem (4 + 2) annulation of 1-perimidines with vinylene carbonate and alkynes affords 4,5-disubstituted azaperylene salts, and -alkynyl 1-perimidines undergo an intra- and intermolecular annulation cascade to give 4,5,14-trisubstituted targets. Most of the intermediates were detected by ESI-MS, indicating a convincible mechanism including three possible paths.
View Article and Find Full Text PDFDithienoarsinines: stable and planar π-extended arsabenzenes.
Chem Sci
November 2024
Faculty of Molecular Chemistry and Engineering, Graduate School of Science and Technology, Kyoto Institute of Technology Goshokaido-cho, Matsugasaki, Sakyo-ku Kyoto 606-0962 Japan
Stable planar dithienoarsinines were synthesized and structurally characterized. These compounds exhibit monomeric structures in the solution and solid states, avoiding dimerization, even in the absence of steric protection. They exhibited high global aromaticity with 14 or 22π-electron systems.
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!