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Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
Initial Examinations of the Diastereoselectivity and Chemoselectivity of Intramolecular Silyl Nitronate [3+2]
Katelyn Stevens1, Shik Ki Li1, Emily Kaufman1
1Department of Chemistry and Biochemistry, Augustana University, Sioux Falls, SD 57197, USA.
Abstract:
This study examined the chemoselectivity and diastereoselectivity of silyl nitronate alkenyn-nitroethers in Intramolecular Silyl Nitronate Cycloadditions (ISNCs) to produce isoxazole derivatives with interesting medicinal properties. These reactions resulted in the formation of either dihydrofuro[3,4-c]isoxazolines/isoxazolidines and/or alkynyl moieties attached to 2,5-dihydrofuryl carbonyls. This study also discerned the diastereoselectivities of the resulting cyclic adducts and compared them to previous findings. The reactions were also investigated with Spartan molecular modeling computations to aid in the understanding of any displayed chemo- and/or stereoselectivity. These [3+2]-cycloaddition reactions demonstrated excellent to complete chemospecificity. The cycloadditions also demonstrated remarkable diastereospecificity in that each diastereomer of the nitroethers resulted in the formation of only one of four possible diastereomeric outcomes. The stereochemistry of the major diastereomers did not agree with previously published findings.
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