Topic
Norbornene
About: Norbornene is a research topic. Over the lifetime, 5628 publications have been published within this topic receiving 104495 citations. The topic is also known as: norbornylene & norcamphene.
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TL;DR: The alkylidene generated during the polymerization of endo-DCP was found to form an intramolecular complex, but this complex only affects the rate slightly, suggesting that the cause of the rate difference between the two isomers of DCP is primarily steric in nature.
Abstract: The activation parameters for the ring-opening metathesis polymerization (ROMP) of endo- (1) and exo-dicyclopentadiene (2), endo-1,2-dihydrodicylopentadiene (3), and norbornene (4) in the presence of Grubbs' catalyst were determined using in situ NMR. The exo isomer of DCP was found to be more than an order of magnitude more reactive than the endo isomer. endo-DCP was found to have reactivity similar to its partially saturated counterpart 3, suggesting that the cause of the rate difference between the two isomers of DCP is primarily steric in nature. This interaction is shown to be predominantly entropic and is suspected to originate from an interaction of the penultimate repeat unit and the incoming monomer. Additionally, the alkylidene generated during the polymerization of endo-DCP was found to form an intramolecular complex, but this complex only affects the rate slightly.
231 citations
TL;DR: This review will primarily focus upon the mechanistic aspects of the Catellani reaction, followed by an overview of the synthetic scope of molecules currently accessible with this technology.
Abstract: In the late 1990s Catellani reported a remarkable palladium-catalyzed domino reaction [1] in the presence of norbornene, in which aryl iodides were alkylated at the ortho positions by alkyl halides followed by a Mizoroki-Heck reaction to afford products of type 1 (Scheme 1) [2–4]. The process allowed for the construction of up to three carbon–carbon bonds in a single reaction using simple, commercially available starting materials. We called this process the Catellani reaction, and in the past decade considerable attention has been focused upon unlocking its synthetic potential. This review will primarily focus upon the mechanistic aspects of the Catellani reaction, followed by an overview of the synthetic scope of molecules currently accessible with this technology.
221 citations
TL;DR: In this article, the preparation of four dimeric nickel complexes and three monomeric palladium(II) complexes bearing didentate pyridinylimine ligands is described.
216 citations
TL;DR: The relationship between alkene structure and reactivity in thiol-ene reactions is derived from the results of kinetic modeling and can be directly related to the relative energy of stationary points obtained from electronic structure calculations.
Abstract: The influence of alkene functionality on the energetics and kinetics of radical initiated thiol–ene click chemistry has been studied computationally at the CBS-QB3 level. Relative energetics (ΔH°, ΔH⧧, ΔG°, ΔG⧧) have been determined for all stationary points along the step-growth mechanism of thiol–ene reactions between methyl mercaptan and a series of 12 alkenes: propene, methyl vinyl ether, methyl allyl ether, norbornene, acrylonitrile, methyl acrylate, butadiene, methyl(vinyl)silanediamine, methyl crotonate, dimethyl fumarate, styrene, and maleimide. Electronic structure calculations reveal the underlying factors that control activation barriers for propagation and chain-transfer processes of the step-growth mechanism. Results are further extended to predict rate constants for forward and reverse propagation and chain-transfer steps (kP, k–P, kCT, k–CT) and used to model overall reaction kinetics. A relationship between alkene structure and reactivity in thiol–ene reactions is derived from the results ...
216 citations
TL;DR: The development of a facile ring-opening olefin metathesis route to alkaline anion exchange membranes via the copolymerization of a tetraalkylammonium-functionalized norbornene with dicyclopentadiene is reported.
Abstract: We report the development of a facile ring-opening olefin metathesis route to alkaline anion exchange membranes via the copolymerization of a tetraalkylammonium-functionalized norbornene with dicyclopentadiene. The thin films generated are mechanically strong and exhibit high hydroxide conductivities and exceptional methanol tolerance.
215 citations