The molecules of the title compound, C26H15N3S, have a pentacyclic ring system which is almost planar, with the central ring in a flattened boat conformation. The folding angle between the two quinoline rings is 6.75 (7) degrees. The 14-phenyl substituent is in a quasi-axial conformation, while the 14-cyano substituent is in a quasi-equatorial conformation with respect to the thiopyran ring. The S...C-C(phenyl) and S...C-C(CN) angles are 116.8 (2) and 129.3 (2) degrees, respectively. The plane of the phenyl group is nearly coplanar with the plane bisecting the dihedral angle of the pentacyclic ring system.
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http://dx.doi.org/10.1107/S0108270105009832 | DOI Listing |
J Am Chem Soc
December 2024
State Key Laboratory of Chemical Biology, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, China.
Here, we report the enantioselective total syntheses of four diepoxy--kaurane diterpenoids including (-)-Macrocalin B, (-)-Acetyl-macrocalin B, and (-)-Isoadenolin A and the revised structure of (-)-Phyllostacin I, which hinges on the strategic design of a regioselective and stereospecific trapping of a highly reactive [3.2.1]-bridgehead enone intermediate via a tethered intramolecular Diels-Alder reaction.
View Article and Find Full Text PDFChemistry
December 2024
Organocatalysis Research Group, Institute of Organic Chemistry, HUN-REN Research Centre for Natural Sciences, 2. Magyar tudósok krt., H-1117, Budapest, Hungary.
A concise, bioinspired, and enantioselective synthesis of (-)-hunterine A, an odd 6/7/6/6/5 pentacyclic natural product, is described. The key step in the synthesis of this complex structure is an interim-template directed 6-exo selective epoxide ring-opening reaction, which is interwoven with a hydrolysis step of the indolenine hemiaminal template to create the unusual 7-membered azepine bridge motif. Our work not only refines the previously proposed biogenetic pathway, but also reveals the possible stereochemical prerequisite of the unique skeletal rearrangement, which provides a vantage point for understanding how (-)-hunterine A is likely to be generated in nature.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Department of Chemistry, University of California, Berkeley, Berkeley, California 94720, United States.
In this report, we detail two distinct synthetic approaches to calyciphylline A-type alkaloids himalensine A and daphenylline, which are inspired by our analysis of the structural complexity of these compounds. Using MolComplex, a Python-based web application that we have developed, we quantified the structural complexity of all possible precursors resulting from one-bond retrosynthetic disconnections. This led to the identification of transannular bonds as especially simplifying to the molecular graph, and, based on this analysis, we pursued a total synthesis of himalensine A from macrocyclic intermediates with planned late-stage transannular ring formations.
View Article and Find Full Text PDFFront Pharmacol
October 2024
Department of Pharmacy, Wuhan No.1 Hospital, Wuhan, China.
Bacterial infections and antibiotic resistance pose significant public health challenges globally. Natural products serve as valuable sources for discovering antimicrobial agents. Planch, a folk medicine, is traditionally used to treat various inflammatory diseases.
View Article and Find Full Text PDFJ Environ Manage
November 2024
National and Local Joint Engineering Research Center for Ecological Treatment Technology of Urban Water Pollution, College of Life and Environmental Science, Wenzhou University, Wenzhou, 325035, China. Electronic address:
High valent metal species, including Mn(III), Fe(IV) and Cu(III), have been identified as key intermediates in the degradation of pollutants in many advanced oxidation processes. However, unlike Mn(III) and Fe(IV), the current exploration of the reaction activity and selective oxidation mechanism of Cu(III) towards pollutants with different structures is still quite limited. Herein, the copper(III) periodate was synthesized to investigate the reactivity towards six sulfonamide antibiotics (SAs) including typical two pentacyclic structures (sulfamethoxazole (SMX) and sulfathiazole (STZ)) and four hexacyclic structures (sulfadiazine (SDZ), sulfamerazine (SMR), sulfamonomethoxine (SMM) and sulfapyridine (SPD)).
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