A novel spirocyclization has been developed for the construction of functionalized spirooxindole pyran via Lewis acid promoted Prins cyclization. The reaction proceeds through formation of a single diastereoisomer with high stereoselectivity. This approach can be used to construct biologically important substituted spirooxindole as well as fluorinated pyran scaffolds.
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http://dx.doi.org/10.1021/acs.joc.5b00249 | DOI Listing |
Angew Chem Int Ed Engl
January 2025
Sichuan University, West China School of Pharmacy, Renmin Sout Road, 3rd Section, 17#, 610041, Chengdu, CHINA.
Bryostatins are a family of marine natural products that have garnered significant interests, as evidenced by over 40 clinical trials. However, their extremely low natural abundance has severely limited further research. Despite significant efforts, which have led to the total synthesis of seven bryostatin members by eight independent research groups, these complex molecules present persistent challenges for stereocontrolled, large-scale, and especially divergent synthesis.
View Article and Find Full Text PDFOrg Biomol Chem
January 2025
Univ Rennes, CNRS, ISCR - UMR 6226, F-35000 Rennes, France.
A straightforward and highly diastereoselective synthesis of -4-hydroxypiperidines is presented. This method allows access to C2 and C4 substituted piperidines, bearing a tetrasubstituted carbon stereocenter at C4. -Disubstituted homoallylic amines and ketoaldehydes as carbonyl partners have been rarely used in aza-Prins cyclizations, expanding the scope of this reaction.
View Article and Find Full Text PDFEuropean J Org Chem
November 2024
Department of Chemistry, University of Rochester, Rochester, NY 14627.
This manuscript describes a study of diverse reaction outcomes that stem from the ionization of -alkynyl-Prins adducts. Experimental results have demonstrated unexpected behavior in the nitrogen-containing systems compared to the analogous oxygen derivatives derived from -Prins/-Nazarov sequences. In-depth experimental studies and computational analysis revealed an intricate mechanism involving competing -Nazarov and -Nazarov pathways.
View Article and Find Full Text PDFAcc Chem Res
December 2024
State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, and Chemical Biology Center, Peking University, 38 Xueyuan Road, Beijing 100191, China.
J Org Chem
October 2024
Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati-781039, Assam, India.
A metal-free, Lewis acid approach for the regioselective synthesis of dihydropyranoquinoline scaffolds has been unveiled. The methodology employs a cascade alkynyl Prins-aza-Michael reaction sequence to deliver the products in good to excellent yields. The strategy features mild reaction conditions, broad substrate scope, and high functional group tolerance.
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