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Review
. 2016 Jan 20;21(1):E117.
doi: 10.3390/molecules21010117.

NHC Backbone Configuration in Ruthenium-Catalyzed Olefin Metathesis

Veronica Paradiso  1 , Chiara Costabile  2 , Fabia Grisi  3
Affiliations
Review

NHC Backbone Configuration in Ruthenium-Catalyzed Olefin Metathesis

Veronica Paradiso et al. Molecules. .

Abstract

The catalytic properties of olefin metathesis ruthenium complexes bearing N-heterocyclic carbene ligands with stereogenic centers on the backbone are described. Differences in catalytic behavior depending on the backbone configurations of symmetrical and unsymmetrical NHCs are discussed. In addition, an overview on asymmetric olefin metathesis promoted by chiral catalysts bearing C₂-symmetric and C₁-symmetric NHCs is provided.

Keywords: NHC ligands; metathesis; ruthenium catalysts; stereogenic centers.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Commercial Grubbs’ and Hoveyda-Grubbs’ second generation catalysts.
Figure 2
Figure 2
NHC-Ru complexes with N-(S)-phenylethyl groups and syn or anti methyl groups on the backbone.
Scheme 1
Scheme 1
Representative RCM, CM and ROMP metathesis reactions.
Figure 3
Figure 3
Catalysts with anti NHC backbone.
Figure 4
Figure 4
Complexes with olefinic moieties on the NHC.
Figure 5
Figure 5
Diastereoselective RRM of 7 with catalyst 6-synGII.
Figure 6
Figure 6
Catalysts with syn and anti methyl groups on the NHC backbone.
Scheme 2
Scheme 2
ROMP of 13 promoted by catalysts 7-GII, and 8-antiGII.
Scheme 3
Scheme 3
Macrocyclic RCM to form 14–17.
Figure 7
Figure 7
Macrocyclic RCM products 14–17.
Figure 8
Figure 8
Catalysts with syn phenyl groups on the NHC backbone.
Figure 9
Figure 9
Macrocyclic RCM products 14 and 18.
Figure 10
Figure 10
Catalysts with unsymmetrical NHCs and syn or anti phenyl substituted backbone.
Figure 11
Figure 11
RCM to form cycloolefins 2, 10 and 12.
Figure 12
Figure 12
Catalysts 12-GII–15-GII bearing monodentate NHCs with anti backbone.
Scheme 4
Scheme 4
Asymmetric ring-closing metathesis reactions.
Figure 13
Figure 13
Catalysts 16-GII–18-GII bearing monodentate NHCs with anti backbone.
Scheme 5
Scheme 5
Asymmetric ring-opening cross metathesis.
Scheme 6
Scheme 6
Asymmetric cross-metathesis.
Figure 14
Figure 14
Catalysts bearing C1-symmetric monodentate NHC.
Figure 15
Figure 15
Rotational isomers of 19-antiHGII.
Scheme 7
Scheme 7
Asymmetric ring closing metathesis of 26 and 28 catalyzed by 21-antiGII.
Scheme 8
Scheme 8
Asymmetric ring closing metathesis of 30 and 32 catalyzed by 22-antiGII.
Scheme 9
Scheme 9
Asymmetric ring closing metathesis of 34 catalyzed by 11-antiGII and 11-antiHGII.
Figure 16
Figure 16
Catalyst 23-antiHGII with chiral bidentate NHC.
Figure 17
Figure 17
Catalysts with backbone-monosubstituted NHCs.
Scheme 10
Scheme 10
AROCM of 36 with allyltrimethylsilane in the presence of 25-GII.
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References

    1. Grubbs R.H. Handbook of Metathesis. Volume 1–3 Wiley-VCH; Weinheim, Germany: 2003.
    1. Connon S.J., Blechert S. In: Ruthenium Catalysts and Fine Chemistry. Dixneuf P.H., Bruneau C., editors. Volume 11. Springer; Heidelberg, Germany: 2004. pp. 93–124.
    1. Fürstner A. Olefin Metathesis and Beyond. Angew. Chem. Int. Ed. 2000;39:3012–3043. doi: 10.1002/1521-3773(20000901)39:17<3012::AID-ANIE3012>3.0.CO;2-G. - DOI - PubMed
    1. Hoveyda A.H., Zhugralin A.R. The remarkable metal-catalysed olefin metathesis reaction. Nature. 2007;450:243–251. doi: 10.1038/nature06351. - DOI - PubMed
    1. Deshmuhk P.H., Blechert S. Alkene metathesis: The search for better catalysts. Dalton Trans. 2007;38:2479–2491. doi: 10.1039/b703164p. - DOI - PubMed

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