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The general scheme is given by scheme 1:
When the reaction is intramolecular it is called ring-closing enyne metathesis or RCEYM (scheme 2):
The carbene is a tungsten carbonyl when used in stoichoimetric amounts (1 equivalent) yields 41% of the phenanthrene 3.2 and when used in catalytic amounts phenanthrene 3.3. The stereoselectivity of this reaction is large with the metal atom exclusively adding to one of the alkyne carbon atoms in the initial reaction step.
The reaction mechanism for this reaction is outlined in scheme 4:
In the first catalytic cycle the alkyne group of enyne 4.1 forms a metallacyclobutene intermediate 4.3 with carbene 4.2 with R' and R' ' any organic group required to stabilized it. In the next step the metathesis step is reversed with formation of a new double bond and a new carbenic center in 4.4. The ring-closing step takes place when this center reacts with the alkene group to a metallacyclobutane 4.5 as in a regular olefin metathesis reaction. The butadiene group forms in the last step with expulsion of a new methylene carbene, initiating the next cycle but now with R' = H and R' ' = H.
This is the proposed "yne-then-ene" mechanism. Evidence for an "ene-then-yne" pathway is beginning to emerge, especially for ruthenium based catalytic systems.
The driving force for this conversion is the formation of a thermodynamically stable conjugated butadiene.
Enyne metathesis reactions are accelerated by ethylene as is demonstrated in the reaction displayed in scheme 5:
|This article is licensed under the GNU Free Documentation License. It uses material from the Wikipedia article "Enyne_metathesis". A list of authors is available in Wikipedia.