Dibenzocycloheptanones (dibenzotropones) were prepared by Brønsted acid mediated intramolecular alkyne-carbonyl metathesis (ACM) reactions. The cyclization precursors are readily available by Sonogashira reaction of 2-bromobenzoyl chloride with terminal alkynes, followed by Suzuki reactions with benzaldehydes. The ACM reactions are highly modular and atom economic and allow for the construction of two regioisomeric series of dibenzotropones.
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http://dx.doi.org/10.1021/acs.joc.1c01132 | DOI Listing |
Chemistry
August 2024
State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, 163 Xianlin Avenue, 210023, Nanjing, Jiangsu, China.
Molecules
May 2024
Institute of Chemistry, University Rostock, Albert-Einstein-Str. 3a, 18059 Rostock, Germany.
Ullazines and their π-expanded derivatives have gained much attention as active components in various applications, such as in organic photovoltaic cells or as photosensitizers for CO photoreduction. Here, we report the divergent synthesis of functionalized diazaullazines by means of two different domino-reactions consisting of either a Povarov/cycloisomerization or alkyne-carbonyl metathesis/cycloisomerization protocol. The corresponding quinolino-diazaullazine and benzoyl-diazaullazine derivatives were obtained in moderate to good yields.
View Article and Find Full Text PDFJ Org Chem
February 2024
Institute for Chemistry, University of Rostock, Albert-Einstein-Straße 3a, 18059 Rostock, Germany.
A series of 4- and 10-benzoyl-1-azapyrenes were prepared by a combination of Pd-catalyzed cross-coupling reactions and Brønsted-acid-mediated alkyne-carbonyl-metathesis (ACM). The photophysical and electrochemical properties of the products were studied and compared to theoretical results.
View Article and Find Full Text PDFChemistry
November 2023
State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, 163 Xianlin Avenue, Nanjing, Jiangsu, 210023, China.
Alkyne-carbonyl metathesis is a type of carbon-carbon forming reaction involving the construction a carbon-carbon double bond and a carbonyl group in one transformation. Herein, a Au(I)-catalyzed ring-closing alkyne-carbonyl metathesis protocol has been developed to make densely substituted γ-butenolides from propargyl α-ketoesters. It features 100 % atom economy, excellent substrate flexibility and benign functional group tolerance.
View Article and Find Full Text PDFSci Adv
June 2023
School of Biotechnology and Health Sciences, Wuyi University, Jiangmen, Guangdong 529020, China.
Chiral ketones and their derivatives are useful synthetic intermediates for the synthesis of biologically active natural products and medicinally relevant molecules. Nevertheless, general and broadly applicable methods for enantioenriched acyclic α,α-disubstituted ketones, especially α,α-diarylketones, remain largely underdeveloped, owing to the easy racemization. Here, we report a visible light photoactivation and phosphoric acid-catalyzed alkyne-carbonyl metathesis/transfer hydrogenation one-pot reaction using arylalkyne, benzoquinone, and Hantzsch ester for the expeditious synthesis of α,α-diarylketones with excellent yields and enantioselectivities.
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