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DOI: 10.1055/a-1896-3987
MnVI-NP–Catalyzed Generation of Nitrile Oxides: Easy Access to Isoxazolines and Isoxazoles via Stereoselective 1,3-Dipolar Cycloaddition Reactions
Research funding by the University Grants Commission (UGC) is gratefully acknowledged.
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Abstract
The versatility and effectiveness of MnVI-NPs as a catalyst is examined for the generation of nitrile oxides from aldoximes and subsequent 1,3-dipolar cycloaddition reactions. This synthetic protocol features fast reaction convergence under benign reaction conditions, operational simplicity, and the use of inexpensive precursors; it avoids the use of acids or bases. The strategy offers excellent chemo-, regio-, and diastereoselectivity in the 1,3-dipolar cycloaddition reaction of in situ generated nitrile oxides with alkenes and alkynes.
Key words
manganese - nanoparticles - nitrile oxides - 1,3-dipolar cycloadditions - isoxazolines - isoxazolesSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1896-3987.
- Supporting Information
Publication History
Received: 14 June 2022
Accepted after revision: 08 July 2022
Accepted Manuscript online:
11 July 2022
Article published online:
02 August 2022
© 2022. The Author(s). This is an open access article published by Thieme under the terms of the Creative Commons Attribution-NonDerivative-NonCommercial-License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by-nc-nd/4.0/)
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- 39 Representative procedure for preparation of 3b: Oxime 1 (1 mmol) and alkene 2 (2.5 mmol) were dissolved in CH2Cl2 (10 mL), and MnVI-NPs (13 mg, 5 mol%) and NaIO4 (214 mg, 1 mmol) were added. The mixture was then stirred for 3.5–5.0 h at 25 °C, with the progress of the reaction being monitored by TLC. After completion of the reaction, the solvent was removed under reduced pressure at room temperature. The reaction mixture was filtered and washed with a mixture of ethyl acetate and cold water. The filtrate was transferred to a separatory funnel and extracted with EtOAc (3 × 30 mL). The combined organic extracts were washed with water (3 × 30 mL) and brine (1 × 30 mL) and then dried over anhydrous Na2SO4. After filtration, the solvent was removed under reduced pressure at room temperature. The residue was purified by column chromatography over silica gel (60–120 mesh) with ethyl acetate–petroleum ether as the eluent to furnish pure Δ2-isoxazoline 3b.3-(3,4-Dichlorophenyl)-4,5-dihydroisoxazole-5-carboxylic acid ethyl ester (3b): Rf = 0.6 (1:4 ethyl acetate–petroleum ether); yield: 76% (218 mg, 0.76 mmol); yellow solid; mp 70 °C. 1H NMR (300 MHz, CDCl3): δ = 1.26 (3 H, t, J = 7.2 Hz), 3.49–3.55 (2 H, m), 4.21 (2 H, q, J = 7.2 Hz), 5.09–5.16 (1 H, m), 7.39–7.68 (2 H, m), 7.78 (1 H, s). 13C NMR (75 MHz, CDCl3): δ = 14.1, 38.4, 62.2, 78.6, 125.9, 126.1, 128.7, 130.9, 133.2, 134.7, 154.3, 169.7. FT-IR (KBr): 1030, 1397, 1734, 3140 cm–1. HRMS: m/z calcd for C12H12Cl2NO3 [M+ + H]: 288.0194; found: 288.0190.
For the first report on 1,3-dipoles and 1,3-dipolar cycloaddition reactions, see:
For reports of sugar-based organic nanostructured materials, see: