Research On Oxidative Reaction Of Allyl Tertiary Alcohol

α,β-unsaturated ketones not only have a certain pharmacological function, but also serve as a kind of synthetic intermediates which are widely used in the fields of medicine, pesticide and spices.oIn order to achieve the 1, 3-migration of carbonyl, the most important things are the convertion of α,β-unsaturated ketones to corresponding alcohols by metal reagents, and then complement the reaction by oxidative rearrangement. However,many reagents employed for these oxidation processes are expensive, sensitive to both air and moisture or using transition metal under harsh conditions. In this paper,an usful method with the Phthaloyl peroxide as an oxidant is descriped for oxidative rearrangement of 2-oxo-allyl compounds.the optimum reaction condition is as follows: substrates (1 equiv.) phthaloyl peroxide (1.5 equiv.), in 1,2-dichloroethane at 80 ℃ for 4h. With optimum procedure in hand, substrates of this protocol were investigated, the reaction affords a broad range of corresponding products in moderate to good yields with good functional group tolerance. It is worth mentioning that when reactions were treated with potassium persulfate, unexpected double bond migration products were obtained in good yields.Based on relevant reports in the literature and our results, a plausible reaction mechanism for this oxidative rearrangement of 2-oxo-allyl compounds has been proposed.