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]}.

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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

• The 1,3-Wittig rearrangement
• The Smiles rearrangement

References