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1,2-Wittig rearrangement



A 1,2-Wittig rearrangement is a categorization of chemical reactions in Organic chemistry, and consists of a 1,2-rearrangement of an ether with an alkyllithium compound [1] [2].

Additional recommended knowledge

The intermediate product is an alkoxy lithium salt and the final product an alcohol. When R2 is a good leaving group and electron withdrawing functional group such as a cyanide (CN) group, [3] this group is eliminated and the corresponding ketone is formed.

Reaction mechanism

The reaction mechanism centers on the formation of a free radical pair with lithium migrating from the carbon atom to the oxygen atom. The R radical then recombines with the ketyl [4] .

The alkyl group migrates in the order of thermodynamical stability methyl < primary alkyl < secondary alkyl < tertiary alkyl in this is line with the radical mechanism. The radical-ketyl pair is short lived and due to a solvent cage effect some isomerizations take place with retention of configuration.

With certain allyl aryl ethers a competing reaction mechanism takes place [4]. The reaction of allyl phenyl ether 1 with sec-butyllithium at -78°C gives the lithiated intermediate 2 which on heating to -25°C only shows the rearranged product 5 but not 4 after trapping the lithium alkoxide with trimethylsilyl chloride. This result rules out a radical-ketyl intermediate 3a in favor of the Meisenheimer complex 3b. Additional evidence for this mechanism is provided by the finding that with a para tert-butyl substituent the reaction is retarded.


See also

References

  1. ^ G. Wittig, L. Löhmann, Ann. 550, 260 (1942)
  2. ^ G. Wittig, Experientia 14, 389 (1958).
  3. ^ Preparation of aryl benzyl ketones by [1,2]-Wittig rearrangement Alan R. Katritzky, Yuming Zhang, Sandeep K. Singh Arkivoc p. 146-150 2002 (vii) link
  4. ^ a b Wittig Rearrangement of Lithiated Allyl Aryl Ethers: A Mechanistic Study Sven Strunk, Manfred Schlosser European Journal of Organic Chemistry Volume 2006, Issue 19 , Pages 4393 - 4397 doi:10.1002/ejoc.200600304
 
This article is licensed under the GNU Free Documentation License. It uses material from the Wikipedia article "1,2-Wittig_rearrangement". A list of authors is available in Wikipedia.
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