Curing Synthetic Metathesis Ailments with Small Doses of Acid

William, A.D; Lee, A. C.-H. “Acid Mediated Ring Closing Metathesis: A Powerful Synthetic Tool Enabling the Synthesis of Clinical Stage Kinase Inhibitors” CHIMIA 2015, 69, 142-145 There’s an adage in total synthesis that “every nitrogen in a molecule adds one year to candidate’s PhD” – in other words “synthetic targets with nitrogens are challenging.” This […]

Reactions of Amines with 2nd Generation Hoveyda-Grubbs Type Catalysts

Ireland, B. J.; Dobigny, B. T.; Fogg, D. E. “Decomposition of a Phosphine-Free Metathesis Catalyst by Amines and Other Bronsted Bases: Metallacyclobutane Deprotonation as a Major Deactivation Pathway” ACS Catal. 2015 5 (8) 4690-4698 [DOI: 10.1021/acscatal.5b00813] Rationally expanding the functional group tolerance of an organometallic catalyst requires a detailed understanding of the mechanism(s) contributing to […]

Enabling Post-Synthetic Modification of Polymers with Metathesis

García-Loma, R.; Albéniz, A. C. “Poly(w-bromoalkylnorbornenes-co-norbornene) by ROMP-Hydrogenation: a Robust Support Amenable to Post-Polymerization Functionalization” RSC Adv. 2015, 5, 70244. Introducing functionality into a polymer is often synthetically challenging. The ability to rapidly generate a diverse array of polymers in a controlled fashion from a common intermediate is highly desirable, because polymers featuring different functional […]

Controlling the “Light” Path to Metathesis

Levin, E.; Mavila, S.; Eivgi, O.; Tzur, E.; Lemcoff, N.G. “Regioselective Chromatic Orthogonality with Light-Activated Metathesis Catalysts” Angew. Chem. Int. Ed. 2015, Advance Article. DOI: 10.1002/anie.201500740 The control of molecular bond formation is fundamental to synthetic chemists. Recently, a creative synthetic route for selective ring formation by utilizing different wavelengths to orthogonally control a reaction […]

Two Reactions for the Price of One Olefin Metathesis Catalyst

“In tandem or alone: a remarkably selective transfer hydrogenation of alkenes catalyzed by ruthenium olefin metathesis catalysts” G. K. Zieli?ski, C. Samoj?owicz, T. Wdowik and K. Grela, Org. Biomol. Chem., 2015, 13, 2684 DOI: 10.1039/C4OB02480J Chemists are always searching for ways to rapidly construct complex molecules from relatively simple starting materials and avoid tedious purification […]

Olefin Metathesis in Self-Healing Materials

Neal, J. A.; Mozhdehi, D.; Guan, Z. “Enhancing Mechanical Performance of a Covalent Self-Healing Material by Sacrificial Noncovalent Bonds” J. Am. Chem. Soc. 2015, 137, 4846-4850. Self-healing materials have been an objective of extensive research for obvious reasons. Most polymers, regardless of their application, are exposed to external stress that may cause them to undergo […]

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 […]