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1611781 
Journal Article 
Intermolecular Olefin Cross-Metathesis Initiated by the Umpolung of Enol Ethers 
Okada, Y; Chiba, K 
2012 
1 
Yuki Gosei Kagaku Kyokaishi
ISSN: 0037-9980 
70 
7 
701-710 
Japanese 
WOS:000306393500003 
Electrochemical approaches have proven to be effective for
regulating either one or two electron transfers at the surface of the electrodes that afford not
only various functional group transformations, but also a wide variety of carbon-carbon bond
forming reactions. Especially, the anodic oxidation of electron-rich olefins generates their
radical cations, which are then trapped by a variety of nucleophiles, leading to a number of
interesting cyclizations. These anodic transformations are initiated by the umpolung processes
that normally nucleophilic electron-rich olefins are anodically oxidized to give electrophilic
radical cations to react with second nucleophiles. Meanwhile, unactivated olefins have been found
to act as carbon nucleophiles in lithium perchlorate/nitromethane electrolyte solutions that can
be used to construct intermolecular carbon-carbon bonds. The use of enol ethers as electron-rich
olefins has led to the formation of cyclobutane-like intermediates through which intermolecular
olefin cross-coupling and -metathesis are achieved. 
anodic oxidation; enol ether; unactivated olefin; olefin cross-coupling; olefin cross-metathesis; electron transfer; umpolung