Synthesis of the spiroisoxazoline natural product (+)-calafianin is reported using asymmetric nucleophilic epoxidation and nitrile oxide cycloaddition as key steps. Synthesis and spectral analysis of all calafianin stereoisomers led to unambiguous assignment of relative and absolute stereochemistry.
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http://dx.doi.org/10.1021/ol053115m | DOI Listing |
J Org Chem
December 2023
Department of Chemistry, University of Connecticut, Storrs, Connecticut 06269, United States.
Isoxazolines and 4-membered heterocycles are significant structural motifs in numerous synthetic intermediates and natural products. [3 + 2] Cycloadditions between enol ethers and nitrile oxides have been well studied; however, nitrile oxide cycloadditions with 4-membered heterocycles to give spiroisoxazolines are unreported. Here, we showcase the regio- and diastereoselective [3 + 2] nitrile oxide cycloadditions of 2-methyleneoxetanes, -azetidines, and -thietanes to give an array of 1,6-dioxo-2-azaspiro[3.
View Article and Find Full Text PDFACS Omega
November 2022
IMBE, UMR CNRS 7263, IRD 237, Aix Marseille Université, Avignon Université, Endoume Marine Station, Chemin de la batterie des lions, 13007 Marseille, France.
Sponges are prolific producers of specialized metabolites with unique structural scaffolds. Their chemical diversity has always inspired natural product chemists working in drug discovery. As part of their metabolic filter-feeding activities, sponges are known to release molecules, possibly including their specialized metabolites.
View Article and Find Full Text PDFMolecules
November 2022
Pharmacology Division, CSIR-Indian Institute of Integrative Medicine, Canal Road, Jammu 180001, India.
J Am Chem Soc
November 2022
Institute of Organic Chemistry and Center for Molecular Biosciences, Leopold-Franzens-University Innsbruck, Innrain 80-82, 6020 Innsbruck, Austria.
We report a general synthetic entry to dihydrooxepine-spiroisoxazoline (DOSI) natural products that culminated in the first racemic total synthesis of psammaplysin A. For the synthesis of the unique spirocyclic fragment we employed a strategy that features two key transformations: (1) a diastereoselective Henry reaction/cyclization sequence to access the C7 hydroxylated isoxazoline scaffold in one step and (2) a regioselective Baeyer-Villiger ring expansion to install the fully substituted dihydrooxepine and avoid the risk of a previously observed oxepine-arene oxide rearrangement. The overall synthesis proceeds in 13 steps from an inexpensive starting material.
View Article and Find Full Text PDFJ Nat Prod
September 2022
Department of Chemistry, University of Riau, Faculty of Mathematics and Natural Sciences, Pekanbaru 28293, Indonesia.
Examination of the MeOH extract of the sponge, cf. , Berquist 1995 collected near Ningaloo Reef, Western Australia for selective acetylcholinesterase (AChE) inhibitors, yielded five new bromotyrosine alkaloids, methyl purpuroceratates A and B ( and ), purpuroceratic acid C (), and ningalamides A and B ( and ). The structures of - share the dibromo-spirocyclohexadienyl-isoxazoline (SIO) ring system found in purealidin-R, while ketoxime is analogous to ianthelline and purpurealidin I.
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