An unprecedented nucleophilic addition/cyclization/aromatization cascade of basic chemicals, i.e., aromatic alkenes/alkynes, trimethylsilyl cyanide and N,N-disubstituted formamide, has been developed to give a series of multisubstituted pyrroles in moderate to good yields with high regioselectivities. This reaction not only reveals a new reaction mode for α-aminonitriles, but also provides a new and efficient cyclization pattern for the synthesis of multisubstituted pyrroles as well as their derivatives, which might facilitate related biological studies.
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http://dx.doi.org/10.1021/acs.orglett.6b01883 | DOI Listing |
Bioorg Chem
March 2024
Laboratory of Medicinal Chemistry, Department of Pharmacy, University of Patras, Patras, GR-26500, Greece. Electronic address:
Herein, we describe the rational design, synthesis and in vitro functional characterization of new heme-dependent, direct soluble guanylyl cyclase (sGC) agonists. These new compounds bear a 1H-pyrazolo[3,4-c]pyridin-7(6H)-one skeleton, modified to enable efficient sGC binding and stimulation. To gain insights into structure-activity relationships, the N6-alkylation of the skeleton was explored, while a pyrimidine ring, substituted with various C5'-polar groups, was installed at position C3.
View Article and Find Full Text PDFOrg Lett
October 2023
Department of Applied Chemistry, Kyung Hee University, Yongin 17104, Korea.
The oxidative alkenylation reaction of α-aminoalkyl C(sp)-H bonds has been investigated with ()-1,2-bis(sulfonyl)ethenes. The catalytic process of iron-polypyridyl complexes drives the single-electron oxidation of dialkyl anilines, resulting in the formation of α-aminoalkyl radical species. Subsequent cascades of radical addition and elimination reactions ensue, ultimately leading to the generation of sulfonylated allylic amine products.
View Article and Find Full Text PDFChem Sci
July 2023
State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences 345 Lingling Road Shanghai 200032 China
Pyrroles, furans, and thiophenes are important structural motifs in biologically active substances, pharmaceuticals and functional materials. In this paper, we disclose an efficient synthetic strategy for the rapid construction of multisubstituted pyrroles, furans, and thiophenes NXS mediated desulfonylative/dehydrogenative cyclization of vinylidenecyclopropanes (VDCPs). The advantages of this method include wide substrate range, high efficiency and synthetic usefulness of the heterocyclic products under metal-free and mild conditions.
View Article and Find Full Text PDFChemistry
May 2023
Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory of Rare Earth Materials Chemistry and, Applications & Key Laboratory of Bioorganic Chemistry and, Molecular Engineering of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, P. R. China.
As the key intermediates in metal-promoted/catalyzed C-C bond coupling reactions of nitriles and alkynes, azametallacyclopentadienes, M(N=CR -CR =CR ), are an important class of azametallacycles. Although the first authentic azametallacyclopentadienes were documented in 1986, their chemistry towards solid-state structures, intrinsic reactivity, and synthetic application was rarely investigated for a long time. At the beginning of this century, seminal works about the applications of azametallacyclopentadienes in the synthesis of heterocycles, including multi-substituted pyridines, isoquinolines, furans, and pyrroles were reported.
View Article and Find Full Text PDFJ Org Chem
January 2023
Department of Chemistry (BK21 Four), Research Institute of Natural Science, Gyeongsang National University, Jinju 52828, Korea.
An efficient, tandem one-pot approach to synthesize multisubstituted 2-acylpyrroles from readily prepared -tosyl triazoles and 2-hydroxymethylallyl carbonates is reported. The reaction proceeds via Rh(II)-catalyzed O-H insertion, [3,3]-sigmatropic rearrangement, Pd(0)-catalyzed oxidative addition, intramolecular cyclization, DBU-promoted E1cB elimination, double bond isomerization, and aromatization, enabling the disconnection and formation of multiple bonds in one reactor. The approach represents a highly regioselective way to access di-, tri-, and tetra-substituted H pyrroles with high efficiency.
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