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Stereoselective construction of sterically hindered oxaspirocycles via chiral bidentate directing group-mediated C(sp3)–O bond formation

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Abstract

The systematic investigation of chiral bidentate auxiliaries has resulted in the discovery of a chiral 2,2-dimethyl-1-(pyridin-2-yl)propan-1-amine-derived directing group that enables stereoselective palladium(II)-catalyzed intramolecular C(sp3)–O bond formation. This new chiral directing group exhibited high reactivity in the activation of methylene C(sp3)–H bonds with excellent levels of stereoselectivity (a diastereomeric ratio of up to 39 : 1), which allowed the construction of a wide range of oxaspirocycles. Mechanistic investigations were also conducted to elucidate the reaction mechanism and understand the origin of the diastereoselectivity. DFT calculations suggest that only modest levels of diastereoselectivity are accomplished at the rate-determining C–H metalation–deprotonation step and the d.r. is further enriched at the reductive elimination step.

Graphical abstract: Stereoselective construction of sterically hindered oxaspirocycles via chiral bidentate directing group-mediated C(sp3)–O bond formation

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Publication details

The article was received on 31 Oct 2017, accepted on 26 Nov 2017 and first published on 27 Nov 2017


Article type: Edge Article
DOI: 10.1039/C7SC04691J
Citation: Chem. Sci., 2018, Advance Article
  • Open access: Creative Commons BY license
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    Stereoselective construction of sterically hindered oxaspirocycles via chiral bidentate directing group-mediated C(sp3)–O bond formation

    Y. Kim, S. Kim, D. Kang, T. Sohn, E. Jang, M. Baik and S. Hong, Chem. Sci., 2018, Advance Article , DOI: 10.1039/C7SC04691J

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