Recent advances in the application of the isoxazoline route to aldols in the synthesis of natural products

Natural Product Reports, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Covering: 2000 to 2024The cycloaddition of nitrile oxides with olefins (NOC), followed by reductive cleavage the resulting isoxazolines, has been widely recognised as a convenient and powerful synthetic strategy for constructing aldol motif in natural product synthesis. Different modes NOC (intermolecular, fused bridged intramolecular) enable synthesis diverse isoxazoline products, which can be converted into highly substituted cyclic acyclic frameworks. This review examines advances this field over past 25 years. More than 50 total syntheses are discussed, encompassing various classes compounds, including macrolides, alkaloids, terpenoids, steroids, pseudosugars, sulfolipids some others. Moreover, basic aspects methodology outlined, methods generation ring cleavage, well stereochemical models intramolecular oxide cycloaddition.

Language: Английский

Expedient Cyano‐hydroxylation of Alkenes Enabled by Halogen Atom Transfer Induced Radical Ring‐Opening Elaboration of 3‐Bromo‐isoxazoline Cycloadducts

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: May 19, 2025

Comprehensive Summary Herein, we present a highly efficient one‐pot, two‐step synthesis of β ‐hydroxy nitrile scaffolds, which possess both significant synthetic value and notable biological activity, starting from readily accessible alkenes. This methodology relies crucially on the seamless integration regioselective (3+2) cycloaddition reaction, employing commercially available 1,1‐dibromoformaldoxime as 1,3‐dipole precursor, with subsequent halogen atom transfer‐induced radical ring‐opening elaboration resulting 3‐bromo‐2‐isoxazoline cycloadducts. protocol is featured by mild reaction conditions, broad alkene scope various derivatizations obtained cyano‐hydroxylation products, offering versatile practical pathway to accessing multi‐functionalized molecules.

Language: Английский

Merging Paired Electrolysis and Copper Catalysis Enables Electrochemical Arylation of Aziridine for the Synthesis of 1,2-Amino Tertiary Alcohols

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: May 26, 2025

1,2-Amino alcohols are omnipresent in bioactive molecules. Conventional approaches to this motif require multistep reactions. Herein, we develop an electrochemical strategy for copper-catalyzed convergent paired electrolysis. By selectively cleaving the C-N bond of 2-aryl-1-tosylaziridines with electron-deficient aromatics as aryl source, 1,2-amino tertiary alcohol scaffold is rapidly constructed. This method features mild reaction conditions, large-scale preparation, and a lack sacrificial electrodes. Experimental studies DFT calculations indicate that tends toward radical cross-coupling.

Language: Английский