Activation of Olefins by Anodically Generated halogen Active Species and Its Application

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Activation of olefins by oxidation using anodically generated halogen active species was studied, and the following reactions were exploited. 1.We have already found that the reaction of stirene derivatives with anodically generated iodine active species [I^+]/TMOF in trimethyl orthoformate (TMOF) gave phenylacetic acid derivatives. We found this time that TMOF was essential as a solvent or a co-solvent with methylene chloride, ethyl acetate, and so no for the formation of phenylacetic acid derivatives. 2.We found a new ring contraction reaction of cyclic amines by utilizing cyclic enamines prepared by anodic oxidation of cyclic amines. Also, [I^+]/TMOF was found to promote the ring contraction reaction. 3.A new method of the prepapration of beta-aryl-substituted cyclic amines was exploited. Namely, beta-haho-alpha-methoxylation of cyclic enamines, the alpha-arylation, and silver ion treatment of the products gave beta-aryl-substituted cyclic amines. By this method, alkaloids such as mesembrine were prepared. 4.Optically acitive 1-acetyl-2-methoxycarbonyl-5-tosylaminopiperidine, a key intermediate for the synthesis of slaflamine, was prepared from L-lysine by utilyzing anodic oxidation. 5.We succeeded in the introduction of oxo group into beta-position of cyclic amines, and could prepare delta-aminolevulinic acid. Exploitation of optically active halogen species and a ring contraction of cyclic enol ethers are remained to be carried out as important subjects of this study.