A new process for the [4 + 2] annulation of donor-acceptor cyclopropanes with acetylenes under the effect of anhydrous GaCl using 1,2-zwitterion reactivity was elaborated. The reaction opens access to substituted dihydronaphthalenes, naphthalenes, and other fused carbocycles. The direction of the reaction can be efficiently controlled by temperature.
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http://dx.doi.org/10.1021/acs.joc.7b00209 | DOI Listing |
Nat Commun
January 2025
College of Chemistry, Beijing Normal University, Beijing, 100875, P.R. China.
Developing donor-acceptor [n]cycloparaphenylenes (D-A [n]CPPs) with multiple emissions from different emissive states remains challenging yet crucial for achieving white-light emission in single-molecule. Here, we report our explorations into acceptor engineering of quinone-based D-A [10]CPPs (Nq/Aq/Tq[10]CPPs) via a post-lateral annulation using Diels-Alder reactions of oxTh[10]CPP. X-ray analysis reveals that Nq[10]CPP displays a side by side packing via naphthoquione stacking while Aq[10]CPP adopts an intercalated conformation through anthraquinone interaction.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100, Copenhagen Ø, Denmark.
The introduction of 4,5-dihydroazuleno[2,1,8-ija]azulene as a central core between two 1,4-dithiafulvene (DTF) units provides a novel class of extended tetrathiafulvalene (TTF) electron donors. Herein we present the synthesis of such compounds with the azulenoazulene further expanded by annulation to benzene, naphthalene, or thiophene rings. Moreover, unsymmetrical donor-acceptor chromophores with one DTF and one carbonyl at the central core are presented.
View Article and Find Full Text PDFJ Org Chem
December 2024
School of Chemistry and Chemical Engineering, Yangzhou University, 180 Siwangting Street, Yangzhou 225002, P. R. China.
Efficient synthesis of highly functionalized cyclopentenols with an exocyclic Z double bond was investigated via a (3 + 2) annulation reaction of 2-aroyl-D-A (donor-acceptor) cyclopropanes with alkynoates in the presence of DABCO. This synthetic approach featured a wide range of readily available 2-aroyl-substituted D-A cyclopropanes with diverse functional groups, densely substituted cyclopentenols with two stereogenic centers and an exocyclic double bond in a highly stereocontrolled manner and had operationally simple and mild reaction conditions.
View Article and Find Full Text PDFAdv Mater
January 2025
Center for Ordered Materials, Organometallics and Catalysis (COMOC), Department of Chemistry, Ghent University, Krijgslaan 281-S3, Ghent, 9000, Belgium.
Org Lett
September 2024
Department of Chemistry, M. V. Lomonosov Moscow State University, Leninskie gory 1-3, Moscow 119991, Russia.
Here, we present a new approach for the activation of donor-acceptor cyclopropanes in ring-opening reactions, which does not require the use of a Lewis or Brønsted acid as a catalyst. Donor-acceptor cyclopropanes containing a phenolic group as the donor undergo deprotonation and isomerization to form the corresponding quinone methides. This innovative strategy was applied to achieve (4 + 1)-annulation of cyclopropanes with sulfur ylides, affording functionalized dihydrobenzofurans.
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