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 groups engender different physical properties. On this premise, Albéniz and co-worker utilized olefin metathesis to produce a polymer with a reactive group that can undergo post-synthetic modification to introduce different side chains. This approach allows for rapid access to a library of functionalized polymers.


Employing ruthenium-catalyzed ring opening metathesis copolymerization of norbornene and w-bromoalkylnorbornenes leads to the corresponding polymer 1-Br with an unsaturated backbone. Hydrogenation of 1-Br produced saturated polynorbornenes (1-Br*) containing an alkyl bromide group for further synthetic manipulation (Scheme 1).

To introduce different side chains, reactions of 1-Br* with various nucleophiles produced modified polymers containing cyano, carbamate, thiol, azido, and stannyl groups in high yields (Scheme 2). Moreover, these groups can undergo further chemistry to make different functionalities. In a representative example of this methodology, the azido-containing polymer (1-N3) was subjected to copper-catalyzed 1,3-dipolar cycloaddition (click chemistry) with various alkynes to produce the corresponding triazole products. Specifically, reaction of 1-N3 with phenylacetylene in the presence of catalytic amount of copper at room temperature produced the triazole-containing polymer (1-TAZ) in 99% isolated yield (Scheme 3). The rapid diversification of a common intermediate via established high-yielding reactions to functionalized materials offers many possibilities for creative solutions.



Use of olefin metathesis to generate a polymer containing a reactive functional group that is amenable to further synthetic elaboration is highly attractive and has tremendous potential. One can envision using the vast toolbox of chemical reactions to tether transition metal catalysts, organocatalysts, chemical sensors, and proteins onto these supports for advanced functionalized materials.

Olefin Metathesis at the 250th ACS Meeting

The 250th ACS National Meeting & Exposition is set for the history-rich city of Boston, MA from August 16 – 20, 2015. The theme of the event is “Innovation from Discovery to Application” which fits well with our favorite topic of olefin … [Continue reading]

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 … [Continue reading]

Olefin Metathesis in Self-Healing Materials

ATM self healing

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 … [Continue reading]

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. … [Continue reading]

Olefin Metathesis at the 249th ACS Meeting

The 249th ACS National Meeting & Exposition is fast approaching with Denver, CO preparing to host the biannual event from March 22 – 26, 2015. The theme of this spring’s event is “Chemistry of Natural Resources” which is fitting for the … [Continue reading]

Yves Chauvin, One of Metathesis Greats, Dies at 84

Yves Chauvin, one of the “metathesis greats,” passed away on January 27, 2015 at the age of 84. Winner of the Nobel Prize in Chemistry in 2005, Chauvin was a key player in proposing the metallacyclobutane intermediate of the generally accepted … [Continue reading]

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 … [Continue reading]

Olefin Metathesis at the 248th ACS Meeting

The 248th American Chemical Society National Meeting and Exposition will be held in San Francisco, California from August 10-14, 2014. The theme of this fall’s meeting is “Chemistry and Global Stewardship.” As olefin metathesis has made significant … [Continue reading]