We describe a metal-free strategy to access various α-arylidene cyclopenta[]indoles phosphine-catalysed (3 + 2) annulation of α,β-ynones and 3-nitroindoles. For the first time, the rearomatisation of the indole nucleus was observed in such an annulative transformation. The method was extended to the synthesis of an antimalarial natural product, bruceolline E.
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http://dx.doi.org/10.1039/d2ob02180c | DOI Listing |
J Org Chem
January 2025
Peptide Chemistry Research Institute, K. N. Toosi University of Technology, P.O. Box 15875-4416, Tehran 19697-64499, Iran.
Herein, we disclose a novel, mild, transition-metal-free approach to synthesizing diversely functionalized isothiocyanates from the corresponding isocyanide precursors, achieving high to excellent yields (up to 97%). The current method sheds light on the reactivity of pyridinium 1,4-zwitterionic thiolates as an unprecedented sulfur source strikingly distinct from their previously known reactivity in ionic annulation reactions, showcasing an innovative approach to organic synthesis.
View Article and Find Full Text PDFOrg Biomol Chem
January 2025
Key Laboratory for Green Organic Synthesis and Application of Hunan Province, Key Laboratory of Environmentally Friendly Chemistry and Application of Ministry of Education, College of Chemistry, Xiangtan University, Xiangtan 411105, China.
Herein, we report a cascade annulation of readily available isocyanobiaryls with simple aldehydes photoredox catalysis, providing a straightforward approach towards valuable 6-hydroxyalkylated phenanthridines. Mechanistic studies indicated the generation of a key acyl radical from aldehydes by hydrogen atom abstraction with a bromine radical. This protocol exhibits exceptional chemoselectivity, excellent tolerance of various functional groups and mild reaction conditions.
View Article and Find Full Text PDFOrg Biomol Chem
January 2025
Mulliken Center for Theoretical Chemistry University of Bonn Beringstr. 4, 53115 Bonn, Germany.
A novel HSO-catalyzed ANRORC-type rearrangement of pyrazinones to imidazoles proceeding through pyridazino[]annulation with simultaneous introduction of a pyrazole ring at position 2 of the imidazole system has been developed, which offers efficient and expedited access to new biheterocyclic systems - 2-(pyrazol-3-ul)imidazoles and 2-(pyrazol-3-yl)imidazo[4,5-]pyridazines. Diverse bi--heterocyclic systems with the imidazo[4,5-]pyridazine-4,7-diamine moiety could be obtained in excellent yield when 5,6-dicyano-3-(2-oxo-2-ethyl)pyrazin-2(1)-ones interact with hydrazines the selective spiro-formation in a tandem ring-opening/ring-closing process, which allowed the simultaneous construction of five new C-N bonds. This new method is compatible with an array of functional groups, proceeds under mild reaction conditions with the involvement of commercially available reagents.
View Article and Find Full Text PDFACS Cent Sci
January 2025
Department of Chemistry, Zhejiang University, Hangzhou 310058, China.
Recently, nickel catalysts have garnered considerable attention for their efficacy and versatility in asymmetric catalysis, attributed to their distinctive properties. However, the use of cost-effective and sustainable divalent nickel catalysts in C-H activation/asymmetric alkene insertion poses significant challenges due to the intricate control of stereochemistry in the transformation of the tetracoordinate C-Ni(II) intermediate. Herein, we report a Ni(II)-catalyzed enantioselective C-H/N-H annulation with oxabicyclic alkenes.
View Article and Find Full Text PDFJ Org Chem
January 2025
School of Science, China Pharmaceutical University, Nanjing 210009, P. R. China.
An -heterocyclic carbene-catalyzed atroposelective [3 + 3] annulation of alkynyl acylazoliums with benzothiazole derivatives has been developed for the divergent synthesis of axially chiral triaryl 2-pyranones and fused 2-pyridones. The regioselectivity of this protocol depends on the structure of benzothiazoles with three different nucleophilic centers. The obtained axially chiral frameworks represent a new class of arylheterocycle atropisomers, which may be potentially useful in medicinal chemistry.
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