Metathesis reactions

Metathesis reactions are chemical reactions in which two hydrocarbons (alkanes, alkenes or alkynes) are converted to two new hydrocarbons by the exchange of carbon–carbon single, double or triple bonds. These are usually catalyzed by a metal catalyst.

Latest Research and Reviews

  • Research |

    Olefin metathesis is a powerful synthetic method that largely rests on the reactivity of molybdenum- and ruthenium-based catalysts, as alternative metals have not yet been successfully substituted. Here the authors engineer an iron catalyst to effectively perform the stereoselective ring-opening metathesis polymerization of norbornene.

    • Satoshi Takebayashi
    • , Mark A. Iron
    •  & David Milstein
    Nature Catalysis 5, 494-502
  • Research |

    Metathesis reactions involving carbon–carbon double bonds have been well established, but direct metathesis of carbon–carbon single bonds is extremely rare. Now, a ruthenium-catalysed carbon–carbon single-bond metathesis reaction has been developed with unstrained homo-biaryl substrates. The reaction shows wide functional group tolerance and operates via an ‘olefin-metathesis-like’ mechanism.

    • Jun Zhu
    • , Rui Zhang
    •  & Guangbin Dong
    Nature Chemistry 13, 836-842
  • Research
    | Open Access

    Air-sensitive molybdenum olefin metathesis catalysts are known to form stable but inactive adducts with appropriate chelating ligands, but regenerating the active catalyst requires the use of Lewis acids and vigorous conditions. Here, tuning the electron donor capacity of the ligands leads to air-stable solid adducts of tungsten and molybdenum alkylidenes that spontaneously release the active catalysts in solution.

    • Henrik Gulyás
    • , Shigetaka Hayano
    •  & Jordi Benet-Buchholz
  • Research |

    The metathesis of carbon–carbon double bonds is an important tool in organic synthesis and now a similar reshuffling has been carried out with heavier alkene analogues featuring unsymmetrically substituted Ge=Ge double bonds. This reaction enables the synthesis of symmetric molecular digermenes as well as a polymer based on Ge=Ge repeat units.

    • Lukas Klemmer
    • , Anna-Lena Thömmes
    •  & David Scheschkewitz
    Nature Chemistry 13, 373-377
  • Research |

    Biocompatibility plays a crucial role for the development of artificial metalloenzymes (ArMs) for therapeutic applications. This work presents an ArM with a ruthenium catalyst that is protected from physiological glutathione and accumulates in cancer cell lines for metathesis-mediated prodrug activation.

    • Shohei Eda
    • , Igor Nasibullin
    •  & Katsunori Tanaka
    Nature Catalysis 2, 780-792
  • Research |

    Nitriles are widely used in chemistry and are found in many bioactive compounds but, despite recent advances, there are no broadly applicable approaches for the synthesis of di- or tri-substituted alkenyl nitriles. New catalytic cross-metathesis strategies now allow direct access to a wide range of Z- or E-di-substituted cyano-substituted alkenes and their tri-substituted variants.

    • Yucheng Mu
    • , Thach T. Nguyen
    •  & Amir H. Hoveyda
    Nature Chemistry 11, 478-487

News and Comment

  • News & Views |

    Carbon–carbon single bonds are generally among the least reactive chemical bonds. While olefin metathesis reactions are well established, direct metathesis of C–C single bonds is rare. Now, a C–C single bond metathesis reaction has been developed, forming cross-biaryl products from unstrained homo-biaryl compounds.

    • Michael M. Gilbert
    •  & Daniel J. Weix
    Nature Chemistry 13, 818-820
  • News & Views |

    Carbonyls and alkenes, two of the most common functional groups in organic chemistry, generally do not react with one another. Now, a simple Lewis acid has been shown to catalyse metathesis between alkenes and ketones in a new carbonyl olefination reaction.

    • Elisabeth T. Hennessy
    •  & Eric N. Jacobsen
    Nature Chemistry 8, 741-742
  • News & Views |

    Metathesis reactions can be used to make carbon–carbon double bonds — bar one isomeric class. By using new catalysts and balancing out the stabilities of intermediates in the reaction, the elusive isomers can be made. See Article p.461

    • Daesung Lee
    Nature 471, 452-453
  • News & Views |

    Olefin metathesis is a flexible and efficient method for making carbon–carbon bonds and has found widespread application in academia and industry. Now, a detailed mechanistic study looking at key catalytic intermediates offers new insight into this reaction, and may prove useful in the development of more active and selective catalysts.

    • Jennifer A. Love
    Nature Chemistry 2, 524-525
  • Research Highlights |

    A Brønsted acid co-catalyst is the key to the synthesis of furans by alkene cross-metathesis.

    • Laura Croft