Oxidation of Allylic Alcohols using the GreicoDess-Martin Periodinane and IBX.
Alibhai, Irfan S.
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The oxidative rearrangement oftertiary allylic alcohols has traditionally been performed using PCC (pyridinium chlorochromate), which is limited in industrial use due to its many harmful effects. This paper investigates the use of a newer oxidizing agent, the Greico-Dess-Martin Periodinane (GDMP) to perform the same reaction. It was found that when the GDMP was used with pyridinium p-toluenesulfonate (PPTS) as an additive, the oxidative rearrangement was in fact possible, though an elimination product was also formed, lowering yields and completing an otherwise simple procedure. In order to eliminate the secondary product, the use of I-hydroxy-I ,2benziodoxol- 3(lH)-one I-oxide (IBX), a precursor the better-known Dess-Martin Periodinane was investigated. Again the reaction was shown to be possible when IBX was used with PPTS as an additive, but again it was complicated by the formation of an elimination product. Finally, as a secondary task, the use of IBX as a selective oxidizing agent in the oxidation ofprimary and secondary allylic alcohols to their corresponding a,(3unsaturated carbonyls was investigated. The results showed that IBX, when used with PPTS as an additive, could in fact perform this reaction in common organic solvents in fair to good yields while the IBX remained insoluble. This discovery allows for IBX to be used as a selective oxidizing agent in a wider range ofreactions without having to use DMSO, in which IBX is soluble, as a solvent.