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Ruthenium in Catalysis pp 1–17Cite as

Cyclometalated Ruthenium Alkylidene Complexes: A Powerful Family of Z-Selective Olefin Metathesis Catalysts

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Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 48))

Abstract

The past 5 years have witnessed an enormous growth in the field of Z-selective olefin metathesis. The development of a new class of cyclometalated ruthenium-based catalysts has extended the utility of olefin metathesis to the synthesis of useful Z-olefin-containing small molecules, polymers, and natural products. This review highlights the recent advances in the area of Z-selective olefin metathesis employing cyclometalated ruthenium alkylidene catalysts, with particular focus on its applications and mechanistic basis. A deeper understanding of structure–activity relationships should aid in the future design of even more active and selective olefin metathesis catalysts.

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Abbreviations

Adm:

Adamantyl

AROCM:

Asymmetric ring opening/cross metathesis

CM:

Cross metathesis

Dipp:

2,6-Diisopropylphenyl

EPA:

Environmental Protection Agency

Mes:

Mesityl

mRCM:

Macrocyclic ring closing metathesis

NHC:

N-heterocyclic carbene

NMR:

Nuclear magnetic resonance

Piv:

Pivaloyl

RCAM:

Ring closing alkyne metathesis

RCM:

Ring closing metathesis

ROMP:

Ring opening metathesis polymerization

TON:

Turnover number

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Acknowledgments

Financial support was provided by the NIH (R01-GM031332), the NSF (CHE-1212767), the NDSEG (graduate fellowship to LER), and the NSERC of Canada (postdoctoral fellowship to VMM). We are grateful to Dr. Jeff Cannon, Dr. John Hartung, Dr. Raul Navarro, and Brendan Quigley for helpful discussions associated with the drafting of this manuscript.

Author information

Authors and Affiliations

  1. Arnold and Mabel Beckman Laboratories of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, 91125, USA

    Vanessa M. Marx, Lauren E. Rosebrugh, Myles B. Herbert & Robert H. Grubbs

Authors
  1. Vanessa M. Marx
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  2. Lauren E. Rosebrugh
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  3. Myles B. Herbert
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  4. Robert H. Grubbs
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Corresponding author

Correspondence to Robert H. Grubbs .

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Editors and Affiliations

  1. Inst. des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université Rennes1, Rennes, France

    Pierre H. Dixneuf

  2. Inst. des Sciences Chimiques de Rennes, UMR 6226-CNRS-Université de Rennes1, Rennes, France

    Christian Bruneau

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Marx, V.M., Rosebrugh, L.E., Herbert, M.B., Grubbs, R.H. (2014). Cyclometalated Ruthenium Alkylidene Complexes: A Powerful Family of Z-Selective Olefin Metathesis Catalysts. In: Dixneuf, P., Bruneau, C. (eds) Ruthenium in Catalysis. Topics in Organometallic Chemistry, vol 48. Springer, Cham. https://doi.org/10.1007/3418_2014_76

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