Ring-opening carbonyl-olefin metathesis of norbornenes.

Chemical Science
Janis JermaksTristan Lambert

Abstract

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.

References

Jan 12, 2008·Accounts of Chemical Research·Yan Zhao, Donald G Truhlar
Jun 19, 2010·Journal of the American Chemical Society·Robert S PatonK N Houk
Nov 7, 2012·Journal of the American Chemical Society·Allison K GriffithTristan H Lambert
Mar 17, 2015·Accounts of Chemical Research·Maciej A A WalczakPeter Wipf
Jul 4, 2015·Organic & Biomolecular Chemistry·Carmen NájeraMiguel Yus
Apr 28, 2016·Nature·Jacob R LudwigCorinna S Schindler
Jul 20, 2016·Angewandte Chemie·Lina MaZhiping Li
Feb 22, 2017·Journal of the American Chemical Society·Christopher C McAteeCorinna S Schindler
Dec 22, 2017·Angewandte Chemie·Lorenzo Catti, Konrad Tiefenbacher
Jul 13, 2018·Chemical Science·Uyen P N TranThanh V Nguyen
Aug 8, 2018·The Journal of Organic Chemistry·Piotr BanachowiczSzymon Buda
Jan 1, 2017·Synlett : Accounts and Rapid Communications in Synthetic Organic Chemistry·Jacob R Ludwig, Corinna S Schindler
Sep 8, 2018·Angewandte Chemie·Benjamin N Bhawal, Bill Morandi
Oct 3, 2018·ACS Catalysis·Emilia J GrosoCorinna S Schindler
Oct 20, 2018·Chemical Society Reviews·Marc R BeckerCorinna S Schindler
Nov 2, 2018·Chemical Communications : Chem Comm·Shengjun Ni, Johan Franzén
Jan 1, 2019·Journal of the American Chemical Society·Haley AlbrightCorinna S Schindler
Jul 6, 2019·Journal of the American Chemical Society·Carly S HansonJames J Devery
Sep 21, 2019·Angewandte Chemie·Miguel Ángel Rivero-CrespoAntonio Leyva-Pérez
Feb 29, 2020·Chemical Science·Paul S RiehlCorinna S Schindler

❮ Previous
Next ❯

Citations

Jun 17, 2021·Chemical Reviews·Haley AlbrightCorinna S Schindler

❮ Previous
Next ❯

Methods Mentioned

BETA
NMR

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.

Related Papers

Trends in Chemistry
Paul S Riehl, Corinna S Schindler
Journal of the American Chemical Society
Allison K GriffithTristan Lambert
© 2021 Meta ULC. All rights reserved