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Acyclic nitronate olefin cycloaddition (ANOC): regio- and stereospecific synthesis of isoxazolines.

ABSTRACT: We report the first demonstrations of intra- and intermolecular acyclic nitronate olefin cycloaddition (ANOC) reactions that enable the highly efficient syntheses of isoxazolines bearing various functional groups. This general approach to accessing γ-lactone fused isoxazolines was hitherto unprecedented. The room temperature transformations reported herein exhibit wide substrate scopes, as evidenced by more than 70 examples, including the generation of five tricyclic isoxazolines. The robustness of this methodology was confirmed by a series of trials that afforded highly functionalized isoxazolines. Both experimental results and density functional theory calculations indicate that these transformations proceed via the in situ formation of acyclic nitronates together with concerted [3+2] cycloaddition and tert-butyloxy group elimination processes to give regio- and stereospecificity.

SUBMITTER: Ma L

PROVIDER: S-EPMC8178991 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature

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Acyclic nitronate olefin cycloaddition (ANOC): regio- and stereospecific synthesis of isoxazolines.

Ma Liang L Kou Luyao L Jin Feng F Cheng Xionglve X Tao Suyan S Jiang Gangzhong G Bao Xiaoguang X Wan Xiaobing X

Chemical science 20201106 2

We report the first demonstrations of intra- and intermolecular acyclic nitronate olefin cycloaddition (ANOC) reactions that enable the highly efficient syntheses of isoxazolines bearing various functional groups. This general approach to accessing γ-lactone fused isoxazolines was hitherto unprecedented. The room temperature transformations reported herein exhibit wide substrate scopes, as evidenced by more than 70 examples, including the generation of five tricyclic isoxazolines. The robustness ...[more]

PMID: 34163811

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