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We report the direct synthesis of new azulene derivatives through gold-catalyzed cyclization reactions. A five-membered ring as backbone in the applied triene-yne substrates turned out to be crucial to induce the 7-endo-dig cyclization mode necessary to trigger azulene formation. The obtained targets are of high interest due to their potential applications in different fields, like organic materials, medicine or cosmetics. UV/Vis spectra and cyclic voltammetry were measured, based on these the electronic properties were determined. Short two or three step sequences towards the applied starting materials make this approach synthetically highly attractive.
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http://dx.doi.org/10.1002/anie.202402481 | DOI Listing |
Nat Commun
January 2025
State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha, China.
(Hetero)polyaryl amines are extensively prevalent in pharmaceuticals, fine chemicals, and materials but the intricate and varied nature of their structures severely restricts their synthesis. Here, we present a selective multicomponent cycloaromatization of structurally and functionally diverse amine substrates for the general and modular synthesis of (hetero)polyaryl amines through copper(I)-catalysis. This strategy directly constructs a remarkable range of amino group-functionalized (hetero)polyaryl frameworks (194 examples), including naphthalene, binaphthalene, phenanthren, benzothiophene, dibenzothiophene, benzofuran, dibenzofuran, quinoline, isoquinoline, quinazoline, and others, which are challenging or impossible to obtain using alternative methods.
View Article and Find Full Text PDFPhys Chem Chem Phys
September 2024
Department of Organic Chemistry, Shahid Beheshti University, Tehran 1983969411, Iran.
DFT calculations are used to disclose the mechanism of Brønsted base-mediated cyclization of (2-alkynylbenzyl)oxy nitriles for the synthesis of benzofuroazepines. In 2015, the synthesis of substituted benzofuroazepines was reported by Zeni a stepwise mechanism known as 7-. However, DFT calculations revealed that the anionic aza 8π-electrocyclization is more favorable than the proposed 7- mechanism.
View Article and Find Full Text PDFJ Org Chem
September 2024
Department of Chemistry and Chemical Sciences, Central University of Jammu, Rahya-Suchani (Bagla), District-Samba, J&K, Jammu 181143, India.
A nucleopalladation-triggered cascade transformation of internal alkynes bearing an amino nucleophile and an electrophilic enone was investigated under unconventional microwave-assisted conditions. Among the three possible pathways, the chloropalladation-triggered domino process proceeded selectively to furnish 3-chloro-1-indenes in good to excellent yields. The reactions under microwave irradiation were completed in 30 min, and the conventional heating required 3-5 h for completion.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
June 2024
Organisch-Chemisches Institut, Heidelberg University, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.
We report the direct synthesis of new azulene derivatives through gold-catalyzed cyclization reactions. A five-membered ring as backbone in the applied triene-yne substrates turned out to be crucial to induce the 7-endo-dig cyclization mode necessary to trigger azulene formation. The obtained targets are of high interest due to their potential applications in different fields, like organic materials, medicine or cosmetics.
View Article and Find Full Text PDFJ Org Chem
November 2023
Department of Chemistry, University of Utah, Salt Lake City, Utah 84112, United States.
Strategies to access the 1,4-diazepindiones heterocyclic core of the TAN-1057 family of natural products revealed a successful gold-catalyzed hydroamination of yneamide tethered amines. The precursor amino-yneamides are derived from easily accessible 1,2-diamines and alkynoic acids and are efficiently cyclized to the corresponding diazepineones.
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