New Remarkably Efficient Ethenolysis Catalysts

Marx, V. M.; Sullivan, A. H.; Melaimi, M.; Virgil; S. C.; Keitz, B. K.; Weinberger, D. S.; Bertrand, G. and Grubbs, R. H. “Cyclic Alkyl Amino Carbene (CAAC) Ruthenium Complexes as Remarkably Active Catalysts for Ethenolysis” Angew. Chem. Int. Ed. 2015, 54, 1919-23 Ethenolysis of seed oils has significant potential as a clean and sustainable […]

The Boomerang is Back in Olefin Metathesis

Bates, J. M.; Lummiss, J. A. M.; C.; Bailey; G. A., and Fogg, D. E. “Operation of the Boomerang Mechanism in Olefin Metathesis Reactions Promoted by the Second-Generation Hoveyda Catalyst” ACS Catal., 2014, 4 (7), 2387-94. No consensus has been reached about the validity of the release-return or Boomerang mechanism involved in the metathesis reactions […]

Examining Polytopal Rearrangements around Ruthenium

Torker, S.; Khan, R.K.M.; Hoveyda, A.M. “The Influence of Anionic Ligands on Stereoisomerism of Ru Carbenes and Their Importance to Efficiency and Selectivity of Catalytic Olefin Metathesis Reactions” J. Am. Chem. Soc. 2014, 136, 3439-3455. For the past 15 years ruthenium catalysts have been a workhorse for olefin metathesis. Chemists have been able to tune […]

Cooperation between a Organometallic Complex and a Metalloenzyme

Denard, C. A.; Huang; H.; Bartlett, M. J., Lu, L.; Tan, Y.; Zhao, H.; and Hartwig, J. F. Angew. Chem. Int. Ed. 2014, 53, 465. Recently, the Hartwig group reported a tandem reaction in which a metalloenzyme and a metathesis catalyst worked cooperatively to yield products which cannot be generated in comparable yield by sequential […]

Ruthenium Initiators Deliver Syndiotactic Polymers

Keitz, B.K.; Fedorov, A.; Grubbs, R.H. “Cis-Selective Ring-Opening Metathesis Polymerization with Ruthenium Catalysts” J. Am. Chem. Soc. 2012, 134, 2040-2043. Rosebrugh, L.E.; Marx, V.M.; Keitz, B.K.; Grubbs, R.H. “Synthesis of Highly Cis, Syndiotactic Polymers via Ring-Opening Metathesis Polymerization Using Ruthenium Metathesis Catalysts” J. Am. Chem. Soc. 2013, 135, 10032-10035. Controlling the stereochemistry of ring opening […]

New Developments in Cis-Selective Ruthenium Metathesis Catalysts

Since Daryl Allen wrote his post in 2011 on the development of the first cis-selective ruthenium catalysts with chelating NHC ligands, a lot of activity and exciting new developments occurred in the area which warrants an update. After the pivalate complex 1 was published1, it was found that the nitrate derivative 2 is more stable and […]

Major Achievement in Olefin Metathesis: First World-Scale Bio-Refinery

July 18, 2013 was a very exciting day for the olefin metathesis community. The first press release from Elevance Renewable Sciences and Wilmar International Limited reported that their joint venture, a $40 million olefin metathesis-based bio-refinery located in Gresik, Indonesia was operational, leading to the first shipments of commercial products to customers.1 The Gresik facility […]

Metathesis Making the Wheels on the Bus Go Round…Over and Over Again

Wolf, S. and Plenio, H. “On the Ethenolysis of End-of-Life Tire Granules” Green Chemistry 2013, 15, 315-319. DOI: 10.1039/c2g36417d If one accepts the old adage “The more things change, the more they stay the same…” is true, does it then follow that “the more things stay the same, the more they (can) change…” Any truthful response […]

New Initiation Mechanism for NHC-Ru Motif in Olefin Metathesis

Urbina-Blanco, C. A.; Poater, A.; Lebl, T.; Manzini, S.; Slawin, A. M. Z.; Cavallo, L.; Nolan, S. P. The Activation Mechanism of Ru-Indenylidene Complexes in Olefin Metathesis. J. Am. Chem. Soc. 2013, 135, 7073-7079. Recent literature accounts have challenged the notion that all olefin metathesis reactions catalyzed by Ru-NHC complexes are identical, beginning with dissociation […]

Terpenes Go ROMPing Into New Materials

Grau, E.; Mecking, S. “Polyterpenes by ring opening metathesis polymerization of caryophyllene and humulene” Green Chemistry 2013, 15, 1112-1115  Polymers are an indispensable commodity within modern society found in all sectors of a consumer economy, such as: materials, pharmaceuticals and energy. Typically derived from non-renewable petroleum sources, polymers account for ~7% of the gas oil […]

Fast Ring Closing Metathesis Reactions at Low Catalyst Loadings

Despite the huge advances in the area of olefin metathesis, better catalysts are still sought to increase the efficiency of ring closing metathesis (RCM) reactions and make them more applicable in industry1. Recently, several modified second-gen Grubbs-Hoveyda catalysts were prepared and tested for RCM by the Plenio group. The goal was to develop faster initiating […]