A photochemical method for the direct synthesis of 1H-pyrazoles from pyridazine N-oxides was developed. This chemistry features a regioselective approach to nonsymmetrically substituted pyridazine N-oxides. Herein, we highlight the first strategic use of photoinduced ring-opening reactions of 1,2-diazine N-oxides for the preparative synthesis of nitrogen heterocycles.
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http://dx.doi.org/10.1021/acs.orglett.6b02562 | DOI Listing |
Adv Sci (Weinh)
December 2024
State Key Laboratory of Organometallic Chemistry and Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, CAS, 345 Lingling Road, Shanghai, 200032, P. R. China.
The transition metal-catalyzed direct coupling reactions involving electron-rich Fischer carbene species are largely underdeveloped and remain a big challenge. Here, a direct coupling reaction of azoles and azine N-oxides is reported with Fischer copper carbene species bearing an α-siloxy group i, which can be in situ generated from acylsilanes catalytically under photoirradiation and redox-neutral conditions. This coupling reaction between electron-rich α-siloxy Fischer Cu-carbene species with hard carbanion nucleophiles may undergo a bimetallic relay process, which is confirmed by the kinetic analysis and in situ NMR analysis.
View Article and Find Full Text PDFInt J Mol Sci
December 2023
A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Division of the Russian Academy of Sciences, 1 Favorsky Street, 664033 Irkutsk, Russia.
The review focuses on recent advances in the methodologies for the formation or introduction of the CHF moiety in -heterocyclic substrates over the past 5 years. The monofluoromethyl group is one of the most versatile fluorinated groups used to modify the properties of molecules in synthetic medical chemistry. The review summarizes two strategies for the monofluoromethylation of -containing heterocycles: direct monofluoromethylation with simple XCHF sources (for example, ICHF) and the assembly of -heterocyclic structures from CHF-containing substrates.
View Article and Find Full Text PDFOrg Lett
March 2022
Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States.
A method for the photoinduced evolution of atomic oxygen from pyridazine -oxides was developed. This underexplored oxygen allotrope mediates arene C-H oxidation within complex, polyfunctional molecules. A water-soluble pyridazine -oxide was also developed and shown to promote photoinduced DNA cleavage in aqueous solution.
View Article and Find Full Text PDFCancer Res
August 2021
Department of Cellular and Molecular Physiology, Yale University School of Medicine, New Haven, Connecticut.
Triple-negative breast cancer (TNBC) is the most aggressive breast cancer subtype with low survival rate and a lack of biomarkers and targeted treatments. Here, we target pyruvate kinase M2 (PKM2), a key metabolic component of oncogenesis. In patients with TNBC, PKM2pS37 was identified as a prominent phosphoprotein corresponding to the aggressive breast cancer phenotype that showed a characteristic nuclear staining pattern and prognostic value.
View Article and Find Full Text PDFCancer Res
March 2020
Department of Surgery, Stanford University School of Medicine, Stanford, California.
Neuroblastoma is a deadly pediatric solid tumor with infrequent recurrent somatic mutations. Particularly, the pathophysiology of tumors without MYCN amplification remains poorly defined. Utilizing an unbiased approach, we performed gene set enrichment analysis of RNA-sequencing data from 498 patients with neuroblastoma and revealed a differentially overexpressed gene signature in MYCN nonamplified neuroblastomas with telomerase reverse transcriptase () gene overexpression and coordinated activation of oncogenic signaling pathways, including E2Fs, Wnt, Myc, and the DNA repair pathway.
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