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Herein we employed ethynylethylene carbonates (EECs) to achieve formal [4 + 1] and [3 + 3] cycloaddition with cyclic 1,3-dicarbonyl compounds. On one hand, EECs with styryl substitution could undergo a remotely controlled enantioselective [4 + 1] cycloaddition reaction. This reaction exhibits good chemoselectivity, regioselectivity, and enantioselectivity. In addition, a [3 + 3] cycloaddition reaction of EECs with cyclic 1,3-dicarbonyl compounds was also achieved, leading to a series of 4-pyrans with impressive chemoselectivity and enantioselectivity.
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http://dx.doi.org/10.1021/acs.orglett.3c03871 | DOI Listing |
Org Lett
September 2025
National Key Laboratory of Advanced Drug Delivery and Release Systems, School of Pharmaceutical Sciences & Institute of Materia Medica, Shandong First Medical University & Shandong Academy of Medical Sciences, Jinan 250117, P. R. China.
A method for the conversion of isoxazoles into thiazoles by skeleton rearrangement has been achieved by an ammonium iodide-catalyzed cycloaddition protocol under mild conditions with a broad substrate scope and good functional group tolerance. Most appealingly, the reaction can proceed smoothly without the addition of any transition metal catalyst. Detailed mechanistic studies, including control experiments and key reaction intermediate characterization, reveal an intermolecular [3+2] cycloaddition reaction pathway.
View Article and Find Full Text PDFOrg Lett
September 2025
College of Chemistry, International Phosphorus Laboratory, Zhengzhou University, Zhengzhou 450001, P. R. China.
The classical 1,3-dipolar cycloaddition reaction predominantly generates five-membered heterocycles through cycloaddition between 1,3-dipoles and unsaturated hydrocarbons, such as alkenes or alkynes. Herein, we report a light-mediated approach that employs saturated amines as alternatives to conventional unsaturated hydrocarbons, enabling their reaction with -imino(iso)quinolinium ylides to achieve efficient synthesis of pyrazolo-fused (iso)quinoline core structures. This method demonstrates operational simplicity, mild reaction conditions, and excellent functional group compatibility.
View Article and Find Full Text PDFChem Asian J
August 2025
Department of Chemistry, National Institute of Technology Tiruchirappalli, Tiruchirappalli, Tamil Nadu, 620015, India.
Pd-catalyzed straight forward [3+2] cycloaddition reaction between spirovinylcyclopropyl-2-oxindole and coumarin/bioisosteres is demonstrated. The resultant products spirooxindolyl-cyclopentane[c]chromanones and structural analogues are obtained in up to 97% yields and > 99:1 dr. The target spirooxindole-cyclopentane architectures with four contiguous stereocenters with high diastereocontrol is differentially influenced by inexpensive 2,2'-bipyridyl ligand and greener solvent EtOH.
View Article and Find Full Text PDFBeilstein J Org Chem
August 2025
Pingshan Translational Medicine Center, Shenzhen Bay Laboratory, Shenzhen, 518118, China.
A formal synthesis of product with tetrahydroflurenone structure as selective estrogen receptor modulator has been realized. The Rh-catalyzed [3 + 2 + 1] reaction of yne-vinylcyclopropanes and CO (20 mmol scale, in 87% yield) for building the 6/5/5 skeleton, and a Heck coupling reaction constructing the [3.2.
View Article and Find Full Text PDFJ Org Chem
August 2025
Department of Chemistry, China Agricultural University, Beijing 100193, P. R. China.
In this paper, we reported a palladium-catalyzed formal (4 + 1) cycloaddition reaction between amido-tethered allylic carbonates and sulfur ylides. The reaction worked well to provide γ-lactam compounds in satisfactory yields and displayed good compatibility to a wide range of functional groups. The synthetic value of the reaction was demonstrated through scale-up reaction and further transformation.
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