These are preliminary reports that have not been peer-reviewed. They should not be regarded as conclusive, guide clinical practice/health-related behavior, or be reported in news media as established information. For more information, please see our FAQs.
metathesis II_sub_Chemrxiv.pdf (3.22 MB)

Ring-Opening Carbonyl-Olefin Metathesis of Norbornenes

submitted on 17.12.2019, 19:39 and posted on 20.12.2019, 12:55 by Janis Jermaks, Phong K. Quach, Zara M. Seibel, Julien Pomarole, Tristan Lambert

A computational and experimental study of the hydrazine-catalyzed ring-opening carbonyl-olefin metathesis of norbornenes is described. Detailed theoretical investigation of the energetic landscape for the full reaction pathway with six different hydrazines revealed several crucial aspects for the design of next-generation hydrazine catalysts. This study indicated that a [2.2.2]-bicyclic hydrazine should offer substantially increased reactivity versus the previously reported [2.2.1]-hydrazine due to a lowered activation barrier for the rate-determining cycloreversion step, a prediction which was verified experimentally. Optimized conditions for both cycloaddition and cycloreversion steps were identified, and a brief substrate scope study for each was conducted. A complication for catalysis was found to be the slow hydrolysis of the ring-opened hydrazonium intermediates, which were shown to suffer from a competitive and irreversible cycloaddition with a second equivalent of norbornene. This problem was overcome by the strategic incorporation of a bridgehead methyl group on the norbornene ring, leading to the first demonstrated catalytic carbonyl-olefin metathesis of norbornene rings.


Enantioselective Bronsted Acid Catalysis with Chiral Cyclopentadienes

National Institute of General Medical Sciences

Find out more...

New Platforms for Catalysis

Directorate for Mathematical & Physical Sciences

Find out more...

Catalytic Platforms Using Aromatic Ions and Other Charged Species

National Institute of General Medical Sciences

Find out more...

American Chemical Society Petroleum Research Fund 53705-ND1


Email Address of Submitting Author


Cornell University



ORCID For Submitting Author


Declaration of Conflict of Interest



Read the published paper

in Chemical Science