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.
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. 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.
The reaction is a formal dyotropic reaction.
Read more about this topic: 1,2-Wittig Rearrangement
Famous quotes containing the words reaction and/or mechanism:
“More and more, when faced with the world of men, the only reaction is one of individualism. Man alone is an end unto himself. Everything one tries to do for the common good ends in failure.”
—Albert Camus (1913–1960)
“The law isn’t justice. It’s a very imperfect mechanism. If you press exactly the right buttons and are also lucky, justice may show up in the answer. A mechanism is all the law was ever intended to be.”
—Raymond Chandler (1888–1959)