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A tandem rhodium(III)-catalyzed system was established to access 3,4-dihydroisoquinolin-1(2)-one by coupling of -methoxy-3-methylbenzamide with 2-methylidenetrimethylene carbonate. This one-pot synthesis protocol processed smoothly under mild reaction conditions. Moreover, a total of 28 examples, broad substrate scope, and high functional-group compatibility were observed. Preliminary mechanism studies were also conducted and demonstrated that the rhodium(III) catalyst played a vital role in the C-H-allylation and N-alkylation cyclization process.
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http://dx.doi.org/10.1021/acs.joc.1c02179 | DOI Listing |
Org Biomol Chem
October 2023
School of Pharmaceutical Sciences & Institute of Materia Medica, Shandong First Medical University & Shandong Academy of Medical Sciences, Jinan 250117, Shandong, P. R. China.
A palladium-catalyzed [4 + 2] cycloaddition of 2-methylidenetrimethylene carbonate or methylene cyclic carbamate with sulfamate-derived cyclic imines has been successfully developed under mild reaction conditions, affording pharmacologically interesting oxazine or hydropyrimidine derivatives in high yields (up to 99% yield). Furthermore, the cycloaddition reactions could be efficiently scaled up and several synthetic transformations were accomplished for the construction of other useful 1,3-oxazine and hydropyrimidinone derivatives.
View Article and Find Full Text PDFOrg Lett
July 2023
Laboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, 4259 Nagatsuta-cho Midori-ku, Yokohama 226-8503, Japan.
Enantioselective dearomative cycloadditions of 4-nitroisoxazoles with vinylethylene carbonate () proceeded in the presence of Pd(dba) and ()-DTBM-SEGPHOS to give the corresponding bicyclic isoxazolines and in good to high yields with excellent enantioselectivities (≤99% ee). This synthetic approach could be applied to -tosyl vinyl aziridine and 2-methylidenetrimethylene carbonate. Further transformations of the resulting cycloadducts and yielded not only its derivatives and but also the novel tetracyclic skeleton .
View Article and Find Full Text PDFOrg Lett
November 2022
School of Pharmacy, Sungkyunkwan University, Suwon 16419, Republic of Korea.
The ruthenium(II)-catalyzed tandem C-H allylation and intramolecular dipolar cycloaddition between azomethine imines and 2-methylidenetrimethylene carbonate is described herein. The initially formed β-substituted allyl fragment could trigger the exotype [3 + 2] cycloaddition with the polar azomethine group, resulting in the formation of bridged tetracycles bearing a hydroxymethylene group at a bridgehead carbon center. A wide substrate scope and broad functional group compatibility were observed.
View Article and Find Full Text PDFJ Org Chem
December 2021
Center for Drug Research and Development, Guangdong Pharmaceutical University, Guangzhou 510006, China.
A tandem rhodium(III)-catalyzed system was established to access 3,4-dihydroisoquinolin-1(2)-one by coupling of -methoxy-3-methylbenzamide with 2-methylidenetrimethylene carbonate. This one-pot synthesis protocol processed smoothly under mild reaction conditions. Moreover, a total of 28 examples, broad substrate scope, and high functional-group compatibility were observed.
View Article and Find Full Text PDFOrg Lett
August 2021
Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084, China.
A novel palladium-catalyzed [4 + 1] cycloaddition to give spirotetrahydrofuran oxindoles has been developed, in which diphenyl 2-oxoindolin-3-yl phosphates were used as the both electrophilic and nucleophilic C synthons at C-3 of the oxindole unit and 2-methylidenetrimethylene carbonate was used as the 1,4-dipole. The cycloannulation was performed at room temperature and provided the corresponding spirotetrahydrofuran oxindoles in good to excellent yields. The present method affords a new strategy for the construction of spirooxindole derivatives with unique three-dimensional structures.
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