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Issue 7, 2015
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Carbene catalyzed umpolung of α,β-enals: a reactivity study of diamino dienols vs. azolium enolates, and the characterization of advanced reaction intermediates

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Abstract

Since their discovery by Bode and Glorius in 2004, N-heterocyclic carbene catalyzed conjugate umpolung reactions of α,β-enals have been postulated to involve the formation of diamino dienols (“homoenolates”) and/or azolium enolates (“enolates”), typically followed by addition to electrophiles, e.g. Michael-acceptors. In this article, we provide evidence, for the first time, for the postulated individual and specific reactivity patterns of diamino dienols (γ-C–C-bond formation) vs. azolium enolates (β-C–C-bond formation). Our study is based on the pre-formation of well defined diamino dienols and azolium enolates, and the in situ NMR monitoring of their reactivities towards enone electrophiles. Additionally, reaction intermediates were isolated and characterized, inter alia by X-ray crystallography.

Graphical abstract: Carbene catalyzed umpolung of α,β-enals: a reactivity study of diamino dienols vs. azolium enolates, and the characterization of advanced reaction intermediates

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Publication details

The article was received on 21 Mar 2015, accepted on 30 Apr 2015 and first published on 30 Apr 2015


Article type: Edge Article
DOI: 10.1039/C5SC01027F
Citation: Chem. Sci., 2015,6, 3706-3711
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    Carbene catalyzed umpolung of α,β-enals: a reactivity study of diamino dienols vs. azolium enolates, and the characterization of advanced reaction intermediates

    V. R. Yatham, Jörg-M. Neudörfl, N. E. Schlörer and A. Berkessel, Chem. Sci., 2015, 6, 3706
    DOI: 10.1039/C5SC01027F

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