Enyne metathesis

Enyne metathesis

An Enyne metathesis is an organic reaction taking place between an alkyne and an alkene with a metal carbene catalyst forming a butadiene. This reaction is a variation of olefin metathesis. ["Enyne Metathesis (Enyne Bond Reorganization)" Diver, S. T.; Giessert, A. J. "Chem. Rev." 2004, "104(3)", 1317-1382. (Review) (DOI|10.1021/cr020009e)]

The general scheme is given by "scheme 1":

:

When the reaction is intramolecular it is called ring-closing enyne metathesis or RCEYM ("scheme 2"):

:

with Y representing oxygen or nitrogen and n an integer.

The reaction was first described in 1985 with the conversion of biphenyl 3.1 to a phenanthrene in "scheme 3": ["Metal-catalyzed rearrangement of alkene-alkynes and the stereochemistry of metallacyclobutene ring opening"Thomas J. Katz and Timothy M. Sivavec "J. Am. Chem. Soc." 1985, "107(3)", 737 - 738. (DOI|10.1021/ja00289a054)]

:

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.

Reaction mechanism

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.

cope

Enyne metathesis reactions are accelerated by ethylene as is demonstrated in the reaction displayed in "scheme 5": ["Enyne ring-closing metathesis on heteroaromatic cations" Ana Núñez, Ana M. Cuadro, Julio Alvarez-Builla and Juan J. Vaquero "Chem. Commun.", 2006, 2690-2692. (DOI|10.1039/b602420c)]

:



400px|Scheme 5. Enyne metathesis synthesis of 2-vinyl-substituted3,4-dihydroquinolizinium salts

In this reaction with the Hoveyda-Grubbs Catalyst, ethylene converts the alkyne group to the corresponding diene group prior to the reaction with the alkene group.

References


Wikimedia Foundation. 2010.

Игры ⚽ Нужно сделать НИР?

Look at other dictionaries:

  • Olefin metathesis — or transalkylidenation is an organic reaction that entails redistribution of alkylene fragments by the scission of carbon carbon double bonds in olefins (alkenes).[1] Its advantages include the creation of fewer sideproducts and hazardous wastes …   Wikipedia

  • Métathèse des énynes — La métathèse des énynes est une réaction organique entre un alcyne et un alcène, catalysée par un carbène métallique et formant un butadiène. Cette réaction est une variation de la métathèse des alcènes[1]. Le schéma général de cette réaction est …   Wikipédia en Français

  • List of organic reactions — Well known reactions and reagents in organic chemistry include Contents: A B C D E F G H I J K L M N O P Q R S T U V W X Y Z    See also   Ext …   Wikipedia

  • Alkyne — Alkynes are hydrocarbons that have at least one triple bond between two carbon atoms, with the formula CnH2n 2. The alkynes are traditionally known as acetylenes or the acetylene series, although the name acetylene is also used to refer… …   Wikipedia

  • Divergent synthesis — In chemistry a divergent synthesis is a strategy with the aim to improve the efficiency of chemical synthesis. It is often an alternative to convergent synthesis or linear synthesis. In one strategy divergent synthesis aims to generate a library… …   Wikipedia

  • Galanthamine total synthesis — ; 2006; 106(1) pp 116 133; (Review) DOI|10.1021/cr040415t] The natural source of galantamine are certain species of daffodil and because these species are scarce and because the isolation of galanthamine from daffodil is expensive (a 1996 figure… …   Wikipedia

  • Grandisol — Grandisol[1][2] IUPAC n …   Wikipedia

  • Olefinmetathese — Die Alkenmetathese (auch Olefinmetathese; von griech. Meta: Wechsel und Thesis: Position), ist eine chemische Reaktion, bei der formal die Alkylidengruppen zwischen Alkenen ausgetauscht werden, wobei statistisch verteilte Produktgemische… …   Deutsch Wikipedia

  • Alkenmetathese — Die Alkenmetathese (auch Olefinmetathese; von griech. Meta: Wechsel und Thesis: Position), ist eine chemische Reaktion, bei der formal die Alkylidengruppen zwischen Alkenen ausgetauscht werden, wobei statistisch verteilte Produktgemische… …   Deutsch Wikipedia

Share the article and excerpts

Direct link
Do a right-click on the link above
and select “Copy Link”