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Exploration of an ambitious new strategy for the total synthesis of the cytotoxic marine natural product amphidinolide F is described, which features fabrication of the core structure from four readily accessible fragments and macrocycle construction through C9-C10 bond formation by intramolecular Stille coupling between an alkenyl iodide and alkenyl stannane. Efficient stereoselective synthesis of each of the four building-blocks and subsequent coupling of them to produce the requisite cyclization precursor has been accomplished, but suitable conditions for high-yielding palladium-mediated closure of the macrocycle to produce the fully protected amphidinolide F ring system have yet to be identified.
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http://dx.doi.org/10.1021/acs.orglett.2c03045 | DOI Listing |
Beilstein J Org Chem
September 2025
School of Pharmaceutical Science, Hengyang Medical School, University of South China, Hengyang 421001, China.
Intelligent controlled-release drug delivery systems that are responsive to various external stimuli have garnered significant interest from researchers and have broad applications in the biomedical field. Aromatic macrocycles, including calixarenes and pillararenes, are considered ideal candidates for the construction of supramolecular drug delivery systems because of their simple synthesis, ease of modification, electron-rich and hydrophobic cavities, and highly selective molecular recognition. In recent years, numerous supramolecular drug delivery systems utilizing aromatic macrocycles have been developed.
View Article and Find Full Text PDFOrg Biomol Chem
September 2025
Department of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK.
Zinc(II) bis(triazolyl)(pyridyl)amine (Zn(BTPA)) complexes on the end of α-amino-iso-butyric acid (Aib) foldamers are able to transfer chirality from bound anions to the helical foldamer body. Zn(BTPA) could be obtained by simple synthetic methodology that allowed a range of functional groups to be installed around the binding site, exemplified with a fluorophore, a macrocyclic bridge and Aib itself. Changing functional group did not prevent chiral ligands from controlling foldamer conformation, although differences in complexation kinetics and equilibria were observed.
View Article and Find Full Text PDFJ Am Chem Soc
September 2025
State Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China.
The discovery of new weak supramolecular interactions and supramolecular synthons is essential for directing self-assembly processes with enhanced precision, diversity, and functionality in complex molecular architectures. Here, we report the controlled self-assembly of diverse supramolecular architectures by a new directional bonding approach through the integration of radical-based dynamic covalent chemistry and supramolecular synthons. A novel macrocyclic synthon, , with a linear direction is constructed via radical-based dynamic covalent bonds from the phenothiazine building block substituted with two dicyanomethyl radicals.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2025
Stoddart Institute of Molecular Science, Department of Chemistry, Zhejiang University, Hangzhou, 310058, P.R. China.
Mechanoresponsive molecular devices are capable of exhibiting dynamic responses to external mechanical stimuli, enabling applications in smart materials, nano-devices, and flexible electronics. However, energy conversion induced by mechanical stimuli requires efficient energy dissipation mechanisms. Traditional methods often involve bond breaking or incomplete energy release, which can lead to device failure during continuous operations.
View Article and Find Full Text PDFJ Am Chem Soc
September 2025
State Key Laboratory of Advanced Materials for Intelligent Sensing and Key Laboratory of Organic Integrated Circuits, Ministry of Education & Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Institute of Molecular Plus, Department of Chemistry, Tianjin University, Tianjin 300072, China.
Incorporating boron atoms into organic macrocycles imparts unique chemical, electronic, and optical properties. The concept of making use of dative boron-nitrogen (B ← N) bonds for the construction of macrocycles has been proposed, but very few examples have been prepared with functional structures, much less pillar-like and other prismatic macrocycles, and their various functionalities have not been fully exploited. Here, we introduce a "functional molecular wall" synthetic protocol based on the self-assembly characteristics of B ← N dative bonds to construct highly symmetrical macrocycles, forming a quasi-pentagonal-shaped macrocycle (named [5]pyBN-) with a pillar-like structure.
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