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:
“In a land which is fully settled, most men must accept their local environment or try to change it by political means; only the exceptionally gifted or adventurous can leave to seek his fortune elsewhere. In America, on the other hand, to move on and make a fresh start somewhere else is still the normal reaction to dissatisfaction and failure.”
—W.H. (Wystan Hugh)
“A mechanism of some kind stands between us and almost every act of our lives.”
—Sarah Patton Boyle, U.S. civil rights activist and author. The Desegregated Heart, part 3, ch. 2 (1962)