Copper-catalyzed dearomatization and difunctionalization of pyridines have been disclosed, in which bromodifluoro--arylacetamide was sliced into five fragments and three or four of them were transferred to pyridine partners. Through this reaction, novel -difluoromethyl-2-imine dihydropyridine derivatives can be conveniently accessed from commercially available 4-amino substituted pyridines. This strategy demonstrates a novel fluorination method featuring high atom economy, environmental friendliness, an easily available catalyst, and simple operation.
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http://dx.doi.org/10.1021/acs.orglett.0c02368 | DOI Listing |
J Org Chem
July 2024
School of Chemical Sciences, National Institute of Science Education and Research (NISER) Bhubaneswar, an OCC of Homi Bhabha National Institute, Khurda 752050, Odisha, India.
Dearomatization is a fundamental chemical reaction that affords complex three-dimensional heterocyclic frameworks. We disclose the first organocatalytic dearomatization of 5-aminopyrazoles, which yields a range of structurally diversified C4-hydroxylated pyrazolines with yields of ≤95% in <1.5 h at room temperature.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
February 2024
State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, China.
Dearomative spirocyclization reactions represent a promising means to convert arenes into three-dimensional architectures; however, controlling the regioselectivity of radical dearomatization with nonactivated arenes to afford the spirocyclizative 1,2-difunctionalization other than its kinetically preferred 1,4-difunctionalization is exceptionally challenging. Here we disclose a novel strategy for dearomative 1,2- or 1,4-amidoximation of (hetero)arenes enabled by direct visible-light-induced homolysis of N-NO bonds of nitrosamides, giving rise to various highly regioselective amidoximated spirocycles that previously have been inaccessible or required elaborate synthetic efforts. The mechanism and origins of the observed regioselectivities were investigated by control experiments and density functional theory calculations.
View Article and Find Full Text PDFJ Am Chem Soc
July 2023
Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, 48149 Münster, Germany.
-Selective C-H functionalization of pyridines holds a significant value but remains underdeveloped. Site-switchable C-H functionalization of pyridines under easily tunable conditions expedites drug development. We recently reported a redox-neutral dearomatization-rearomatization strategy for -C-H functionalization of pyridines via oxazino pyridine intermediates.
View Article and Find Full Text PDFOrg Biomol Chem
May 2023
School of Chemistry & Chemical Engineering, Beijing Institute of Technology (Liangxiang Campus), Beijing 102488, China.
A Lewis acid-catalyzed electrophilic dearomatizative thiocyanation and cyclization of benzofurans with -thiocyanatosuccinimide has been accomplished by Lewis acid catalysis with CuOTf under mild conditions. It was suggested that the electrophilic thiocyanating reagent was activated by CuOTf, and difunctionalization was achieved through a thiocyanation/spirocyclization pathway. Thus, a series of thiocyanato-containing spiroketals were obtained in moderate to high yields.
View Article and Find Full Text PDFChem Rec
July 2023
School of Pharmaceutical Sciences, University of Shizuoka 52-1 Yada, Suruga-ku, Shizuoka, 422-8526, Japan.
Fluorine is an attractive element in the field of pharmaceutical and agrochemical chemistry due to its unique properties. Considering the chiral environment in nature, where enantiomers often show different biological activities, the introduction of fluorine atom(s) into organic molecules to make chiral fluorinated compounds is an important subject. Herein, we describe the story of the development of our chiral carboxylate-based phase-transfer catalysts and their applications for asymmetric fluorocyclizations of alkenes bearing a carboxylic acid, an amide, and an oxime as an internal nucleophile with a dicationic fluorinating reagent, Selectfluor.
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