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. 2011 Jun 8;133(22):8525-7.
doi: 10.1021/ja202818v. Epub 2011 May 12.

Chelated ruthenium catalysts for Z-selective olefin metathesis

Koji Endo  1 , Robert H Grubbs
Affiliations

Chelated ruthenium catalysts for Z-selective olefin metathesis

Koji Endo et al. J Am Chem Soc. .

Abstract

We report the development of ruthenium-based metathesis catalysts with chelating N-heterocyclic carbene (NHC) ligands that catalyze highly Z-selective olefin metathesis. A very simple and convenient procedure for the synthesis of such catalysts has been developed. Intramolecular C-H bond activation of the NHC ligand, promoted by anion ligand substitution, forms the appropriate chelate for stereocontrolled olefin metathesis.

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Figures

Figure 1
Figure 1
Plausible transition states of the intramolecular C-H bond activation in 3a.
Figure 2
Figure 2
X-ray crystal structure and selected bond length of 4a are shown. Displacement ellipsoids are drawn at 50% probability. For clarity, hydrogen atoms have been omitted.
Figure 3
Figure 3
X-ray crystal structure and selected bond length of 4b are shown. Displacement ellipsoids are drawn at 50% probability. For clarity, hydrogen atoms have been omitted.
Figure 4
Figure 4
Plot of conversion versus time for the RCM of 5. Reaction conditions were as follows; 1a: 1.0 mol % catalyst, 0.1 M substrate, 30 °C, CD2Cl2; 4a: 1.0 mol % catalyst, 0.1 M substrate, 30 °C, C6D6; 4b: 5.0 mol % catalyst, 0.1 M substrate, 70 °C, C6D6.
Scheme 1
Scheme 1
Synthesis of 1b
Scheme 2
Scheme 2
Synthesis of 4a
Scheme 3
Scheme 3
Synthesis of 4b
See this image and copyright information in PMC

References

    1. Fürstner A. Angew Chem Int Ed. 2000;39:3012–3043. - PubMed
    2. Trnka TM, Grubbs RH. Acc Chem Res. 2001;34:18–29. - PubMed
    3. Schrock RR. Chem Rev. 2002;102:145–179. - PubMed
    4. Schrock RR, Hoveyda AH. Angew Chem Int Ed. 2003;42:4592–4633. - PubMed
    5. Samojłowicz C, Bieniek M, Grela K. Chem Rev. 2009;109:3708–3742. - PubMed
    6. Vougioukalakis G, Grubbs RH. Chem Rev. 2010;110:1746–1787. - PubMed
    1. Meek SJ, O’brien RV, Llaveria J, Schrock RR, Hoveyda AH. Nature. 2011;471:461–466. - PMC - PubMed
    1. Flook MM, Jiang AJ, Schrock RR, Muller P, Hoveyda AH. J Am Chem Soc. 2009;131:7962–7963. - PMC - PubMed
    2. Flook MM, Gerber LCH, Debelouchina GT, Schrock RR. Macromolecules. 2010;43:7515–7522. - PMC - PubMed
    3. Torker S, Müller A, Chen P. Angew Chem Int Ed. 2010;49:3762–3766. - PubMed
    4. Flook MM, Ng VWL, Schrock RR. J Am Chem Soc. 2011;132:1784–1786. - PubMed
    1. Grubbs RH, editor. Handbook of Metathesis. Wiley-VCH; Weinheim: 2003. pp. s1–3.
    1. Rosen EL, Sung DH, Chen Z, Lynch VM, Bielawski CW. Organometallics. 2010;29:250–256.
    2. Teo P, Grubbs RH. Organometallics. 2010;29:6045–6050.

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