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Allylmetallation of benzoazaheterocycles with allylic derivatives of zinc. Synthesis of 1,4-ethano-2,3-dihydroisoquinolines and allylated heterocycles

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Abstract

Allylmetallation of isoquinolines, quinoline, and quinoxaline with allylic derivatives of zinc was examined for the first time. A convenient procedure was discovered and developed for the synthesis of 1,4-ethano-2,3-dihydroisoquinolines based on the reactions of isoquinolines with allylic derivatives of zinc. This multistage process involves double allylmetallation of the heterocyclic ring followed by cyclization through intramolecular carbometallation of the C=C bond. The structures of three key derivatives of 1,4-ethano-2,3-dihydroisoquinoline were established by X-ray diffraction analysis. The reactions of quinoxaline with allyl- and methallylzinc bromide proceeded stereospecifically to form trans-2,3-diallylated 1,2,3,4-tetrahydroquinoxalines. Heating of quinoline with methallylzinc bromide in THF afforded 4-methallylquinoline in nearly quantitative yield. The initially formed 1,4-metallation product underwent aromatization through elimination of HZnBr.

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Authors and Affiliations

  1. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 119991, Moscow, Russian Federation

    Yu. N. Bubnov, F. V. Pastukhov & Z. A. Starikova

  2. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991, Moscow, Russian Federation

    Yu. N. Bubnov & A. V. Ignatenko

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  1. Yu. N. Bubnov
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  2. F. V. Pastukhov
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  3. Z. A. Starikova
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  4. A. V. Ignatenko
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Bubnov, Y.N., Pastukhov, F.V., Starikova, Z.A. et al. Allylmetallation of benzoazaheterocycles with allylic derivatives of zinc. Synthesis of 1,4-ethano-2,3-dihydroisoquinolines and allylated heterocycles. Russian Chemical Bulletin 50, 2172–2182 (2001). https://doi.org/10.1023/A:1015065721466

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