Thirteen costus-sensitive patients were patch tested with 38 sesquiterpene lactones of five different classes over a two-year period. Cross-reacting agents fell into two chemical categories: (1) those that resembled the primary sensitizer, and (2) those belonging to different skeletal classes. An exocyclic methylene group conjugated to a gamma-lactone was present in both chemicals that cross-reacted and those that did not. The difference between these two groups is that cross-reacting chemicals are not highly substituted, tending to be lipophilic, while those giving negative responses all are highly substituted at the C-8/C-6 position. This functional group may hinder binding of exocyclic methylene with skin protein or the actual antigenic site with an immune receptor cell.
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http://dx.doi.org/10.1001/archderm.116.1.59 | DOI Listing |
Acc Chem Res
January 2025
Department of Chemistry, University of Wisconsin, 1101 University Avenue, Madison, Wisconsin 53706, United States.
ConspectusThe manipulation of strained rings is a powerful strategy for accessing the valuable chemical frameworks present in natural products and active pharmaceutical ingredients. Aziridines, the smallest N-containing heterocycles, have long served as building blocks for constructing more complex amine-containing scaffolds. Traditionally, the reactivity of typical aziridines has been focused on ring-opening by nucleophiles or the formation of 1,3-dipoles.
View Article and Find Full Text PDFJ Nat Prod
December 2024
School of Pharmaceutical Sciences, College of Medical, Pharmaceutical and Health Sciences, Kanazawa University, Kanazawa 920-1192, Japan.
Syzygioblanes A-C (-), isolated from the Indonesian traditional herbal medicine (), are meroterpenoids with a spiro ring formed through a [4 + 2] cycloaddition of the flavanone desmethoxymatteucinol with cyclic sesquiterpenoids. Our ongoing phytochemical investigation of resulted in the isolation of five additional spiro-meroterpenoids, syzygioblanes D-H (-), which are hybrids of the same flavanone with eudesmane/cadinane-type sesquiterpenoids. A possible biosynthetic pathway involves enzymatic dearomative hydroxylation of desmethoxymatteucinol followed by [4 + 2] cyclization of the resulting diene with a cyclic sesquiterpene containing an exocyclic methylene to form the unique spiro ring in the syzygioblane molecule.
View Article and Find Full Text PDFOrg Biomol Chem
October 2024
Departamento de Química Orgánica, Escuela Nacional de Ciencias Biológicas, Instituto Politécnico Nacional, Prolongación de Carpio y Plan de Ayala S/N, 11340 Mexico City, Mexico.
A short, efficient, and stereoselective methodology is described for the synthesis of 5-((dimethylamino)methylene)hydantoins and their conversion into oxoaplysinopsins and parabanic acids. A highly convergent one-pot, two-step reaction between methyl -arylglycinates, isocyanates, and DMFDMA under microwave irradiation provided the corresponding (dimethylamino)methylene hydantoins as a single -stereoisomer in high overall yields. The synthesis of ()-1-(1-phenylethyl) chiral hydantoins, which undergo a stereoselective addition of acetic anhydride, aza-heterocycles, and amines, received special attention.
View Article and Find Full Text PDFOrg Lett
September 2024
Key Laboratory of Biocatalysis & Chiral Drug Synthesis of Guizhou Province, School of Pharmacy, Zunyi Medical University, Zunyi 563000, China.
A facile copper-catalyzed [3 + 2] cycloaddition of -2,2,2-trifluoroethylisatin ketimines with various electron-deficient alkenes to access structurally polyfunctionalized spiro-pyrrolidine-oxindole motifs has been developed. Under the catalytic system, the -2,2,2-trifluoroethylisatin ketimines could be utilized to react with a series of exocyclic alkenes, including 2-acylamino acrylates, 3-methylene-β-lactams, and sterically hindered cycloalkenes represented by cyclobutenone, to obtain a variety of densely functionalized spiro-pyrrolidine frameworks bearing an α-amino acid ester, β-lactam, and cyclobutanone, respectively, in generally good yields with excellent diastereo- and enantioselectivities.
View Article and Find Full Text PDFChempluschem
December 2024
Department of Chemistry, UiT The Arctic University of Norway, Tromsø, 9037, Norway.
Nitroxides are stable organic radicals with exceptionally long lifetimes, which render them uniquely suitable as observable probes or polarising agents for spectroscopic investigation of biomolecular structure and dynamics. Radical-based probes for biological applications are ideally characterized by both robustness towards reductive degradation and beneficial electron spin relaxation parameters. These properties are largely influenced by the molecular structure of the nitroxide scaffold, and also by the conformations it prefers to adopt.
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