Asymmetric synthesis presents many challenges, with the selective formation of chiral bridged polyheterocycles being a notable example. Cycloadditions using bicyclo[1.1.0]butanes (BCB) offer a promising solution along those lines, yet, despite significant advances in that emerging area, asymmetric control has remained limited thus far. Here, we describe an organocatalytic, enantioselective formal (3 + 3)-cycloaddition of BCBs with 1-indol-3-yl((hetero)aryl)methanol derivatives. This approach enables the rapid and efficient synthesis of chiral tetrahydro-1-1,3-methanocarbazole derivatives (34 examples) from readily available starting materials, with very good stereochemical control (up to 98:2 ). Successful scale-up experiments and product modification demonstrated the potential of this methodology. Control experiments and DFT calculations provide insights into the mechanistic pathway.
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http://dx.doi.org/10.1021/jacs.4c14276 | DOI Listing |
J Am Chem Soc
January 2025
Organisch-Chemisches Institut, Universität Münster, Corrensstraße 40, Münster 48149, Germany.
Asymmetric synthesis presents many challenges, with the selective formation of chiral bridged polyheterocycles being a notable example. Cycloadditions using bicyclo[1.1.
View Article and Find Full Text PDFACS Omega
January 2025
Department of Medical Laboratory Sciences, College of Medicine and Health Sciences, Arba Minch University, P.O. Box No. 21, Arba Minch 21, Ethiopia.
The present work focuses on a newly synthesized pyrazolo[3,4-]pyridine prepared by formal [3 + 3] cycloaddition using copper(II) acetylacetonate as the catalyst; efficient and effective mild reactions with high yields were obtained using this method. The synthesized compounds were identified by FT-IR, H and C NMR, and mass spectra (/) analyses. The compounds () were screened for several in vitro and in silico activities.
View Article and Find Full Text PDFJ Org Chem
January 2025
Hubei Key Laboratory of Natural Medicinal Chemistry and Resource Evaluation, School of Pharmacy, Huazhong University of Science and Technology, 13 Hangkong Road, Wuhan, Hubei 430030, People's Republic of China.
A novel copper-catalyzed formal diastereoselective [4 + 3] cycloaddition of 2-arylaziridines and 2-substituted cyclopentadiene was developed. This transformation provided an efficient protocol for the assembly of a highly strained bridged azabicyclo[3.2.
View Article and Find Full Text PDFOrg Lett
January 2025
State Key Laboratory of Applied Organic Chemistry & College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, Gansu 730000, P. R. China.
Herein, we present a visible-light-induced protocol for the synthesis of highly functionalized oxo-bridged oxocine skeletons. This method generates carbenes via visible-light-induced ortho-acyl diazo compounds, which are rapidly intercepted by the oxygen atom of an intermolecular acyl group to form a cyclic 1,3-dipole. The in situ generated highly reactive 1,3-dipole undergoes a facile formal [4 + 3] cycloaddition with alkenyl pyrazolinone, yielding [4.
View Article and Find Full Text PDFChem Sci
November 2024
State Key Laboratory of Chemo/Biosensing and Chemometrics, Advanced Catalytic Engineering Research Center of the Ministry of Education, College of Chemistry and Chemical Engineering, Hunan University Changsha Hunan 410082 P. R. China
Although cycloadditions of bicyclobutanes (BCBs) have emerged as a reliable approach for producing bicyclo[.1.1]alkanes such as azabicyclo[3.
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